Chain polyene group-containing norbornene compound and unsaturated ethylene copolymer using the same

ABSTRACT

The chain polyene-group containing norbornene compound of the invention is represented by the formula [I]: ##STR1## wherein n is an integer of 1 to 5, R 1  is an alkyl group of 1 to 5 carbon atoms, and R 2  and R 3  are each independently a hydrogen atom or an alkyl group of 1 to 5 carbon atoms. 
     The unsaturated ethylene copolymer of the invention is a random copolymer of 30 to 92% by mol of (i) ethylene units, 6 to 70% by mol of (ii) specific α-olefin units and 0.1 to 30% by mol of (iii) units derived from the norbornene compound [I], where the molar ratio of (i)/(ii) is in the range of 40/60 to 92/8 and the unit (iii) is represented by the specific formula, and has an intrinsic viscosity [η] of 0.05 to 10 dl/g. 
     The novel unsaturated ethylene copolymer is excellent in weathering resistance, heat resistance and ozone resistance and has a high vulcanizing rate.

TECHNICAL FIELD

The present invention relates to a novel chain polyene group-containingnorbornene compound and a process for preparing the compound. Moreparticularly, the invention relates to a chain polyene group-containingnorbornene compound suitably used for preparing a novel unsaturatedethylene copolymer being excellent in weathering resistance, heatresistance and ozone resistance and having a high vulcanizing rate, andto a process for preparing the compound.

Further, the invention relates to a novel unsaturated ethylene copolymerof the above properties using the chain polyene group-containingnorbornene compound and to a process for preparing the copolymer.

Furthermore, the invention relates to a rubber composition containingthe unsaturated ethylene copolymer.

BACKGROUND ART

Polyene compounds generally are compounds (monomers) having two or morecarbon-to-carbon double bonds in one molecule, and many polyenecompounds, e.g., 1,3-butadiene, 1,3-pentadiene, 1,4-hexadiene,ethylidene-2-norbornene and dicyclopentadiene, have been hitherto known.

When the polyene compounds are copolymerized with α-olefins such asethylene and propylene, vulcanizable unsaturated ethylene copolymers canbe obtained. Since the unsaturated ethylene copolymers generally haveexcellent weathering resistance, heat resistance and ozone resistance,they have been used for rubber products such as automotive industrialparts, industrial rubber products, insulating materials, building andcivil engineering materials, and rubberized fabrics. Moreover, they havebeen widely used as blending materials for plastics such aspolypropylene and polystyrene.

Examples of the unsaturated ethylene copolymers conventionally usedinclude an ethylene/propylene/5-ethylidene-2-norbornene copolymer, anethylene/propylene/dicyclopentadiene copolymer and anethylene/propylene/1,4-hexadiene copolymer. Of these, theethylene/propylene/5-ethylidene-2-norbornene copolymer has beenparticularly widely used, because it has a higher vulcanizing rate ascompared with other unsaturated ethylene copolymers.

However, the conventional unsaturated ethylene copolymers are nowdesired to be further improved in the vulcanizing rate. That is, theunsaturated ethylene copolymers, for example, even theethylene/propylene/5-ethylidene-2-norbornene copolymer, are low in thevulcanizing rate as compared with diene rubbers such as natural rubbers,styrene/butadiene rubber, isoprene rubber, butadiene rubber and nitrilerubber. Therefore, the co-vulcanizability of the unsaturated ethylenecopolymers with the diene rubbers is insufficient.

Further, the vulcanizing rate of the unsaturated ethylene copolymers islower than that of the diene rubbers, so that it is difficult to preparevulcanized rubbers therefrom with high productivity by shortening thevulcanizing time, lowering the vulcanizing temperature or reducing theenergy consumption in the vulcanization stage.

The vulcanizing rate of the unsaturated ethylene copolymers can beincreased by increasing the amount of a vulcanizing agent used. However,if the unsaturated ethylene copolymers are vulcanized using a largeamount of a vulcanizing agent, the vulcanizing agent sometimes bloomsonto the surface of the resulting vulcanized rubbers, resulting inhygienic disadvantages.

Accordingly, development of a novel polyene compound capable ofpreparing an unsaturated ethylene copolymer being excellent inweathering resistance, heat resistance and ozone resistance and having ahigh vulcanizing rate, and development of an unsaturated ethylenecopolymer using the polyene compound have been desired.

Under such circumstances mentioned above, the present inventors haveearnestly studied polyene compounds and unsaturated ethylene copolymersusing the polyene compounds. As a result, they have found that anunsaturated ethylene copolymer using a specific chain polyenegroup-containing norbornene compound, i.e., an unsaturated ethylenecopolymer having constituent units derived from an α-olefin and aspecific chain polyene group-containing norbornene compound and havingan unsaturated bond, is excellent in weathering resistance, heatresistance and ozone resistance and has a high vulcanizing rate. Basedon this finding, the present invention has been accomplished.

In Japanese Patent Publication No. 42365/1971, there is described aprocess for preparing an olefin copolymer comprising bringing at leastone of ethylene and α-olefins having the formula RCH═CH₂ (R: hydrocarbongroup having 1 to 20 carbon atoms) and a 5-polyenyl-2-norbornenecompound into contact with a coordination catalyst, said5-polyenyl-2-norbornene compound having the following formula: ##STR2##

wherein R¹ and R² are each H or a hydrocarbon group of 1 to carbonatoms, and Q is a hydrocarbon group in which at least one internaldouble bond is situated at the non-conjugated position and all of thedouble bonds are of internal type.

However, the olefin copolymer obtained in the process of the abovepublication is not always sufficient under the circumstances thatunsaturated copolymers being excellent in weathering resistance, heatresistance, ozone resistance and vulcanizing rate and having a goodbalance of these properties are desired.

The present invention is intended to solve such problems associated withthe prior art as described above, and it is an object of the inventionto provide a chain polyene group-containing norbornene compound suitablyused for preparing an unsaturated ethylene copolymer being excellent inweathering resistance, heat resistance and ozone resistance and having ahigh vulcanizing rate, and to provide a process for preparing thecompound.

It is another object of the invention to provide an unsaturated ethylenecopolymer of the above properties and a process for preparing thecopolymer.

It is a further object of the invention to provide a rubber compositioncontaining the unsaturated ethylene copolymer.

DISCLOSURE OF THE INVENTION

The chain polyene group-containing norbornene compound according to theinvention is represented by the formula [I]: ##STR3## wherein n is aninteger of 1 to 5, R¹ a hydrogen atom, or is an alkyl group of 1 to 5carbon atoms, and R² and R³ are each independently a hydrogen atom or analkyl group of 1 to 5 carbon atoms, provided that R¹ and R² are nothydrogen at the same time.

The process for preparing a chain polyene group-containing norbornenecompound according to the invention comprises:

reacting cyclopentadiene with a branched chain polyene compoundrepresented by the formula [III]: ##STR4## wherein n is an integer of 1to 5, R¹ is an alkyl group of 1 to 5 carbon atoms, and R² and R³ areeach independently a hydrogen atom or an alkyl group of 1 to 5 carbonatoms,

to thereby prepare the above-mentioned chain polyene group-containingnorbornene compound.

The unsaturated ethylene copolymer according to the invention ischaracterized in that:

[A] said copolymer is a random copolymer of:

(i) ethylene,

(ii) an α-olefin of 3 to 20 carbon atoms, and

(iii) at least one chain polyene group-containing norbornene compoundrepresented by the above formula [I];

[B] said copolymer comprises:

(i) constituent units derived from ethylene in an amount of 30 to 92% bymol,

(ii) constituent units derived from the α-olefin of 3 to 20 carbon atomsin an amount of 6 to 70% by mol, and

(iii) constituent units derived from the chain polyene group-containingnorbornene compound represented by the above formula [I] in an amount of0.1 to 30% by mol, wherein

(iv) the molar ratio of (i) the constituent units derived fromethylene/(ii) the constituent units derived from the α-olefin of 3 to 20carbon atoms is in the range of 40/60 to 92/8;

[C] the constituent unit derived from the chain polyene-group containingnorbornene compound represented by the above formula [I] has a structurerepresented by the following formula [II]: ##STR5## wherein n is aninteger of 1 to 5, R¹ is an alkyl group of 1 to 5 carbon atoms, and R²and R³ are each independently a hydrogen atom or an alkyl group of 1 to5 carbon atoms; and

[D] said copolymer has an intrinsic viscosity [η], as measured inDecalin at 135° C., of 0.05 to 10 dl/g.

The process for preparing an unsaturated ethylene copolymer according tothe invention comprises

copolymerizing

(i) ethylene,

(ii) an α-olefin of 3 to 20 carbon atoms, and

(iii) at least one chain polyene group-containing norbornene compoundrepresented by the above formula [I],

in the presence of a catalyst formed from a transition metal compound,an organoaluminum compound and/or an ionizable ionic compound, tothereby prepare the above-mentioned unsaturated ethylene copolymer.

In addition to the chain polyene group-containing norbornene compound[I], at least one chain polyene group-containing norbornene compound[I-a] represented by the following formula [I-a] may be contained as thecomponent (iii) of [A] in the unsaturated ethylene copolymer of theinvention, in an amount smaller than that of the compound [I],preferably in an amount of less than 50% by mol, more preferably notmore than 40% by mol, particularly preferably not more than 35% by mol,based on 100% by mol of the total amount of the compound [I] and thecompound [I-a]; ##STR6## wherein, n, R¹, R² and R³ have the samemeanings as in the formula [I].

In this random copolymer, with reference to the above item [B] (iii),the total of the content of the constituent units [II] derived from thechain polyene group-containing norbornene compound represented by theformula [I] and the content of the later-described constituent units[II-a] derived from the chain polyene group-containing norbornerecompound represented by the formula [I-a] is the same amount as in thecase of using the chain polyene group-containing norbornene compound[II] alone, that is, 0.1 to 30% by mol.

The quantity ratio between the constituent units [II] and theconstituent units [II-a] is in proportion to the quantity ratio betweenthe chain polyene group-containing norbornene compounds [I] and [I-a].The constituent units [II-a] are copolymerized in an amount of less than50% by mol, preferably not more than 40% by mol, particularly preferablynot more than 35% by mol, based on 100% by mol of the total of theconstituent units [II] and [II-a].

With reference to the above item [C], the constituent unit derived fromthe chain polyene group-containing norbornene compound represented bythe above formula [I] has a structure represented by the above formula[II], and the constituent unit derived from the chain polyenegroup-containing norbornene compound represented by the above formula[I-a] has a structure represented by the following formula [II-a]:##STR7## wherein n, R¹, R² and R³ have the same meanings as in theformula [II].

The unsaturated ethylene copolymer of the invention can be prepared bycopolymerizing

(i) ethylene,

(ii) an α-olefin of 3 to 20 carbon atoms, and

(iii) at least one chain polyene group-containing norbornene compoundrepresented by the above formula [I] and at least one chain polyenegroup-containing norbornene compound represented by the above formula[I-a] in a smaller amount than that of the chain polyenegroup-containing norbornene compound [I],

in the presence of a catalyst formed from a transition metal compound,an organoaluminum compound and/or an ionizable ionic compound.

The rubber composition according to the invention comprises:

any of the above-mentioned unsaturated ethylene copolymers, and

at least one component selected from the following components (a), (b)and (c):

(a) a reinforcing agent in an amount of not more than 300 parts byweight based on 100 parts by weight of the unsaturated ethylenecopolymer,

(b) a softener in an amount of not more than 200 parts by weight basedon 100 parts by weight of the unsaturated ethylene copolymer, and

(c) a vulcanizing agent.

The chain polyene group-containing norbornene compound according to theinvention can be suitably used as a monomer copolymerizable withα-olefins such as ethylene and propylene when the unsaturated ethylenecopolymer being excellent in weathering resistance, heat resistance andozone resistance and having a high vulcanizing rate is prepared.

The unsaturated-ethylene copolymer according to the invention isexcellent in weathering resistance, heat resistance and ozone resistanceand has a high vulcanizing rate.

BEST MODE FOR CARRYING OUT THE INVENTION

The chain polyene group-containing norbornene compound, the process forpreparing the norbornene compound, the unsaturated ethylene copolymerusing the norbornene compound, the process for preparing the unsaturatedethylene copolymer and the rubber composition containing the unsaturatedethylene copolymer according to the invention are described in detailhereinafter.

Chain Polyene Group-containing Norbornene Compound

The chain polyene group-containing compound [I] according to theinvention is represented by the following formula [I], as describedabove. ##STR8##

In the formula [I], n is an integer of 1 to 5, R¹ is an alkyl group of 1to 5 carbon atoms, and R² and R³ are each independently a hydrogen atomor an alkyl group of 1 to 5 carbon atoms. The numerals 1 to 7, n+3, etc.indicate carbon numbers (positions of substituents).

Examples of the alkyl groups of 1 to 5 carbon atoms include methyl,ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl,n-pentyl and i-pentyl.

Examples of the chain polyene group-containing norbornene compoundsrepresented by the formula [I] (sometimes referred to as "chain polyenegroup-containing norbornene compound [I]" hereinafter) include thefollowing compounds (1) to (24). Of these, the compounds (5), (6), (9),(11), (14), (19) and (20) are preferably employed.

(1) 5-(2-Ethylidene-4-hexenyl)-2-norbornene,

(2) 5-(2-Ethylidene-5-methyl-4-hexenyl)-2-norbornene,

(3) 5-(2-Ethylidene-5-methyl-4-heptenyl)-2-norbornene,

(4) 5-(2-Ethylidene-5-ethyl-heptenyl)-2-norbornene,

(5) 5-(2-Ethylidene-4,5-dimethyl-4-hexenyl)-2-norbornene,

(6) 5-(2-Ethylidene-4,5-dimethyl-4-heptenyl)-2-norbornene,

(7) 5-(2-Ethylidene-4-octenyl)-2-norbornene,

(8) 5-(2-Ethylidene-5-methyl-4-octenyl)-2-norbornene,

(9) 5-(2-Ethylidene-4-propyl-5-methyl-4-hexenyl)-2-norbornene,

(10) 5-(2-Ethylidene-5-heptenyl)-2-norbornene,

(11) 5-(2-Ethylidene-6-methyl-5-heptenyl)-2-norbornene,

(12) 5-(2-Ethylidene-6-nonenyl)-2-norbornene,

(13) 5-(2-Ethylidene-6-methyl-5-nonenyl)-2-norbornene,

(14) 5-(2-Ethylidene-5,6-dimethyl-5-heptenyl)-2-norbornene,

(15) 5-(2-Ethylidene-5,6-dimethyl-5-octenyl)-2-norbornene,

(16) 5-(2-Ethylidene-5,6-dimethyl-5-nonenyl)-2-norbornene,

(17) 5-(2-Ethylidene-5-ethyl-6-methyl-5-nonenyl)-2-norbornene,

(18) 5-(2-Ethylidene-5,6-diethyl-5-octenyl)-2-norbornene,

(19) 5-(2-Ethylidene-7-methyl-6-octenyl)-2-norbornene,

(20) 5-(2-Ethylidene-6,7-dimethyl-6-octenyl)-2-norbornene,

(21) 5-(2-Ethylidene-8-methyl-7-nonenyl)-2-norbornene,

(22) 5-(2-Ethylidene-7,8-dimethyl-7-nonenyl)-2-norbornene,

(23) 5-(2-Ethylidene-9-methyl-8-decenyl)-2-norbornene, and

(24) 5-(2-Ethylidene-8,9-dimethyl-8-decenyl)-2-norbornene.

The chemical formulas of the above compounds (1) to (24) are givenbelow. ##STR9##

The chain polyene group-containing norbornene compound [I] is used as amonomer for preparing the later-described unsaturated ethylenecopolymer, preferably used together with (i) ethylene and (ii) anα-olefin of 3 to 20 carbon atoms. In this case, the chain polyenegroup-containing norbornene compound [I] may be one kind of astereoisomer, e.g., a trans form alone or a cis form alone, or it may bea mixture of stereoisomers, e.g., a mixture of a trans form and a cisform.

The chain polyene group-containing norbornene compound [I] can besuitably used for preparing novel unsaturated ethylene copolymers beingexcellent in weathering resistance, heat resistance and ozone resistanceand having a high vulcanizing rate, as described later.

Next, the process for preparing the chain polyene group-containingnorbornene compound [I] is explained.

Preparation of Chain Polyene Group-containing Norbornene Compound [i]

The process for preparing the chain polyene group-containing norbornenecompound [I] (or the compound [I-a]) is described below in detail.

The chain polyene group-containing norborrene compound [I] of theinvention is prepared by the following process. ##STR10##

That is, as described in Japanese Patent Application No. 154952/1994(filing date: Jul. 6, 1994) filed by the present applicant, ethylene isfirst reacted with a conjugated diene compound [III-a] represented bythe following formula [III-a]: ##STR11## wherein, n is an integer of 1to 5, R¹ is an alkyl group of 1 to 5 carbon atoms, and R² and R³ areeach independently a hydrogen atom or an alkyl group of 1 to 5 carbonatoms,

in the presence of a catalyst comprising a transition metal compound andan organoaluminum compound so as to synthesize a branched chain polyenecompound [III] represented by the following formula [III]: ##STR12##wherein, n, R¹, R² and R³ have the same meanings as in the formula[III-a].

Then, the branched chain polyene compound [III] is reacted withcyclopentadiene (Diels-Alder reaction) as described in Japanese PatentApplication No. 322099/1994 (filing date: Dec. 26, 1994), to therebyobtain the chain polyene group-containing norbornene compound [I].

The steps of the process for preparing the chain polyene-groupcontaining norbornene compound [I] are described in more detail in orderhereinafter.

Preparation of Branched Chain Polyene Compound [III]

The branched chain polyene compound [III] can be prepared by reacting acompound having conjugated diene and represented by the formula [III-a](sometimes referred to as "conjugated diene compound [III-a]"hereinafter) with ethylene.

Examples of the-alkyl groups of 1 to 5 carbon atoms in the formula[III-a] are the same as those described above.

Examples of the conjugated diene compounds represented by the formula[III-a] include the following compounds (1) to (24).

(1) 3-Methylene-1,5-heptadiene,

(2) 6-Methyl-3-methylene-1,5-heptadiene,

(3) 6-Methyl-3-methylene-1,5-octadiene,

(4) 6-Ethyl-3-methylene-1,5-octadiene,

(5) 5,6-Dimethyl-3-methylene-1,5-heptadiene,

(6) 5,6-Dimethyl-3-methylene-1,5-octadiene,

(7) 3-Methylene-1,5-nonadiene,

(8) 6-Methyl-3-methylene-1,5-nonadiene,

(9) 6-Methyl-5-propyl-3-methylene-1,5-heptadiene,

(10) 3-Methylene-1,6-octadiene,

(11) 7-Methyl-3-methylene-1,6-octadiene,

(12) 3-Methylene-1,6-decadiene,

(13) 7-Methyl-3-methylene-1,6-decadiene,

(14) 6,7-Dimethyl-3-methylene-1,6-octadiene,

(15) 6,7-Dimethyl-3-methylene-1,6-nonadiene,

(16) 6,7-Dimethyl-3-methylene-1,6-decadiene,

(17) 7-Methyl-6-ethyl-3-methylene-1,6-decadiene,

(18) 6,7-Diethyl-3-methylene-1,6-nonadiene,

(19) 8-Methyl-3-methylene-1,7-nonadiene,

(20) 7,8-Dimethyl-3-methylene-1,7-nonadiene,

(21) 9-Methyl-3-methylene-1,8-decadiene,

(22) 8,9-Dimethyl-3-methylene-1,8-decadiene,

(23) 10-Methyl-3-methylene-1,9-undecadiene, and

(24) 9,10-Dimethyl-3-methylene-1,9-undecadiene.

Through the above reaction, the branched chain polyene compound [III] isgenerally obtained in the form of a mixture of a trans form and a cisform. The trans form and the cis form can be separated from each otherby means of distillation, though depending on the structure of thebranched chain polyene compound [III].

By the above reaction, a chain polyene compound represented by thefollowing formula [III-b] is sometimes produced as a by-product togetherwith the branched chain polyene compound [III].

    H.sub.2 C═CH--CH.sub.2 --CH═C(CH.sub.3)--(CH.sub.2)n--CR.sup.3 ═CR.sup.2 R.sup.1                                     [III-b]

As the by-product, there may be mentioned, for example,5,9-dimethyl-1,4,8-decatriene, which is produced as a by-product when7-methyl-3-methylene-1,6-octadiene (β-myrcene) is reacted with ethyleneto synthesize EMN (4-ethylidene-8-methyl-1,7-nonadiene).

The by-product can be usually separated by means of distillation.

The reaction of the conjugated diene compound [III-a] with ethylene isconducted for 0.5 to 30 hrs at a temperature of usually 50 to 200° C.,preferably 70 to 150° C., under an ethylene pressure of 1 to 100 kg/cm²,preferably 10 to 70 kg/cm², though these conditions vary depending onthe type of the conjugated diene compound [III-a].

This reaction may be carried out in an atmosphere of an inert gas suchas nitrogen or argon. The reaction can be carried out using no solvent,and however, it may be carried out in the presence of an inerthydrocarbon solvent such as hexane, heptane, octane, nonane, decane,undecane, dodecane, tridecane, toluene or xylene.

This reaction is generally carried out in the presence of a catalyst.Especially when the reaction is conducted in the presence of a catalystcomprising a transition metal compound and an organoaluminum compound,the branched chain polyene compound [III] can be efficiently obtained.

Examples of the transition metal compounds include chlorides of irongroup transition metals, such as iron and ruthenium, cobalt grouptransition metals, such as cobalt, rhodium and iridium, and nickel grouptransition metals such as nickel and palladium, bromides of thesemetals, acetylacetonato salts, 1,1,1,5,5,5- hexafluoroacetylacetonatosalts, and dipivaloylmethane salts. Of these, preferable are chloridesof cobalt, iron, nickel, rhodium and palladium, and particularlypreferable is cobalt chloride.

In the reaction, these transition metal compounds (e.g., transitionmetal chlorides) can be used as they are, but they are preferably usedin the form of transition metal complexes wherein organic ligands arecoordinated to the transition metal compounds. In other words, it ispreferable that an organic compound (coordination compound) capable ofbecoming a ligand of the transition metal is allowed to be present inthe reaction system together with the transition metal compound, or atransition metal complex previously formed from the transition metalcompound and the coordination compound is used.

Examples of the compounds capable of becoming the ligands includebis(diphenyphosphino)methane, 1,2-bis(diphenylphosphino)ethane,1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane,triethylphosphine, tributylphosphine, triphenylphosphine, cyclooctadieneand cyclooctatetraene.

As the complexes wherein organic ligands are coordinated to thetransition metal compounds, preferably employable are[1,2-bis(diphenylphosphino)ethane]cobalt(II) chloride,[1,2-bis(diphenylphosphino)ethane]nickel(II) chloride,bis(triphenylphosphine)nickel(II) chloride, etc.

Examples of the organoaluminum compounds include those used in thepreparation of the later-described unsaturated ethylene copolymer. Ofthese, triethylaluminum is preferably employed. The organoaluminumcompound may be used as it is, or it can be used in the form of atoluene solution or a hexane solution.

In the reaction of the conjugated diene compound [III-a] with ethylene,the transition metal compound is used in an amount of preferably 0.001to 10% by mol, particularly preferably 0.01 to 1% by mol, based on theconjugated diene compound [III-a]. The coordination compound is used inan amount of preferably 0 to 20 times by mol, particularly preferably0.1 to 5 times by mol, as much as the transition metal compound.

The organoaluminum compound is used in an mount of preferably 1 to 200times by mol, particularly preferably 3 to 100 times by mol, as much asthe transition metal compound.

In the present invention, it is preferable that the transition metalcompound (or transition metal complex) is previously contacted with theorganoaluminum compound and the resulting product is used as thecatalyst for the above reaction (reaction of the conjugated dienecompound [III-a] and ethylene).

By virtue of the reaction of the conjugated diene compound [III-a] withethylene, there can be obtained the following branched chain polyenecompound [III]: ##STR13## wherein n, R¹, R² and R³ have the samemeanings as in the aforesaid formula [III-a].

Examples of the branched chain polyene compounds [III] include thefollowing compounds (1) to (24). Of these, the compounds (5), (6), (9),(11), (14), (19) and (20) are preferably employed.

(1) 4-Ethylidene-1,6-octadiene,

(2) 7-Methyl-4-ethylidene-1,6-octadiene,

(3) 7-Methyl-4-ethylidene-1,6-nonadiene,

(4) 7-Ethyl-4-ethylidene-1,6-nonadiene,

(5) 6,7-Dimethyl-4-ethylidene-1,6-octadiene,

(6) 6,7-Dimethyl-4-ethylidene-1,6-nonadiene,

(7) 4-Ethylidene-1,6-decadiene,

(8) 7-Methyl-4-ethylidene-1,6-decadiene,

(9) 7-Methyl-6-propyl-4-ethylidene-1,6-octadiene,

(10) 4-Ethylidene-1,7-nonadiene,

(11) 8-Methyl-4-ethylidene-1,7-nonadiene (EMN),

(12) 4-Ethylidene-1,7-undecadiene,

(13) 8-Methyl-4-ethylidene-1,7-undecadiene,

(14) 7,8-Dimethyl-4-ethylidene-1,7-nonadiene,

(15) 7,8-Dimethyl-4-ethylidene-1,7-decadiene,

(16) 7,8-Dimethyl-4-ethylidene-1,7-undecadiene,

(17) 8-Methyl-7-ethyl-4-ethylidene-1,7-undecadiene,

(18) 7,8-Diethyl-4-ethylidene-1,7-decadiene,

(19) 9-Methyl-4-ethylidene-1,8-decadiene,

(20) 8,9-Dimethyl-4-ethylidene-1,8-decadiene,

(21) 10-Methyl-4-ethylidene-1,9-undecadiene,

(22) 9,10-Dimethyl-4-ethylidene-1,9-undecadiene,

(23) 11-Methyl-4-ethylidene-1,10-dodecadiene, and

(24) 10,11-Dimethyl-4-ethylidene-1,10-dodecadiene.

The chemical formulas of the above compounds (1) to (24) are givenbelow. ##STR14##

These branched chain polyene compounds [III] are used singly or incombination of two or more kinds in the preparation of the chain polyenegroup-containing norbornene compound [I].

The branched chain polyene compound [III] may be a mixture of a transform and a cis form, or it may be a trans form alone or a cis formalone.

Preparation of Chain Polyene Group-containing Norbornene Compound [I]

In the present invention, the branched chain polyene compound [III](also referred to as "non-conjugated triene compound") of the followingformula [III]: ##STR15## wherein, n, R¹, R² and R³ have the samemeanings as described above, is reacted with cyclopentadiene(Diels-Alder reaction) to obtain the chain polyene group-containingnorbornene compound [I] of the following formula [I]: ##STR16## wherein,n is an integer of 1 to 5, R¹ is an alkyl group of 1 to 5 carbon atoms,and R² and R³ are each independently a hydrogen atom or an alkyl groupof 1 to 5 carbon atoms.

When R¹, R² or R³ in the formula [I] is an alkyl group of 1 to 5 carbonatoms, examples of such alkyl groups include methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl andisopentyl.

In the branched chain polyene compound [III] used in the above reaction,R¹ and R² are each an alkyl group of 1 to 3 carbon atoms, particularlypreferably methyl, and R³ is preferably hydrogen.

The cyclopentadiene is generally obtained by subjectingdicyclopentadiene, i.e., a dimer of cyclopentadiene, to thermaldecomposition distillation at a temperature of not lower than 160° C.Therefore, in the reaction of the cyclopentadiene with the branchedchain polyene compound [III] in the present invention, dicyclopentadienecan be used in place of the cyclopentadiene depending on the reactiontemperature used. That is, it is possible that the dicyclopentadiene isthermally decomposed in the reaction system to produce cyclopentadieneand this cyclopentadiene is used in the reaction with the branched chainpolyene compound [III].

The reaction of the cyclopentadiene with the branched chain polyenecompound [III] is carried out under the following conditions, though theconditions vary depending on the type of the branched chain polyenecompound [III] used. 1 part by weight of the branched chain polyenecompound [III] and 0.2 to 4 parts by weight, preferably 0.5 to 3 partsby weight, of the cyclopentadiene are stirred under heating at 50 to250° C., preferably 100 to 200° C., under a pressure of 1 to 100 kg/cm²,preferably 5 to 70 kg/cm², for about 0.5 to 30 hours, in an atmosphereof preferably an inert gas such as nitrogen or argon.

The reaction may be conducted in the presence of a radicalpolymerization inhibitor such as hydroquinone, if needed.

In the reaction of the cyclopentadiene with the branched chain polyenecompound [III], a reaction solvent may be used or may not be used.

Examples of the reaction solvents employable herein include hydrocarbontype solvents, such as hexane, heptane, octane, nonane, decane,undecane, dodecane, tridecane, toluene and xylene; halogenatedhydrocarbon type solvents, such as dichloromethane, dichloroethane anddichlorobenzene; ether type solvents, such as tetrahydrofuran anddioxane; and alcohol type solvents, such as methanol, ethanol,isopropanol and t-butanol. Water is also employable as the reactionsolvent.

The chain polyene group-containing norbornene compound [I] obtained asabove is represented by the aforesaid formula [I]. Examples of the chainpolyene group-containing norbornene compounds [I] are described before.

The chain polyene group-containing norbornene compound [I] generally hasa stereoisomeric structure (endo form and exo form based on the bondingway of chain polyene to the norbornene skeleton, and trans form and cisform based on the substitution way of double bond of the chain polyere).

The structure of the chain polyene group-containing norbornene compound[I] can be determined by mass spectrometry or measurement of infraredabsorption spectrum, proton NMR spectrum, etc.

In the present invention, when the chain polyene group-containingnorbornene compound [I] is used for preparing the later-describedunsaturated ethylene copolymer and the rubber composition containing thecopolymer, the compound [I] may be a mixture of the aforesaid variousnorbornene compounds having stereoisomeric structures or may be acompound of one stereoisomer only.

By the above reaction, the chain polyene group-containing norbornenecompound [I] is usually obtained in the form of a mixture of an endoform and an exo form. The mixture can be separated by means ofdistillation according to necessity.

If the starting polyene compound used in the preparation of the chainpolyene group-containing norbornene compound [I] contains in addition tothe branched chain polyene compound [III] a by-product [III-b] of thefollowing formula [III-b] produced during the synthesis of the branchedchain polyene compound [III],

    H.sub.2 C═CH--CH.sub.2 --CH═C(CH.sub.3)--(CH.sub.2).sub.n --CR.sup.3 ═CR.sup.2 R.sup.1                          [III-b]

the by-product [III-b] is reacted with the cyclopentadiene to produce asa by-product a chain polyene group-containing norbornene compound [I-a]of the following formula [I-a]: ##STR17##

wherein, R¹, R², R³ and n are the same as those in the formula [I].

In the process for preparing an unsaturated ethylene copolymer accordingto the invention, a substance containing a small amount of the chainpolyene group-containing norbornene compound [I-a] in addition to thechain polyene group-containing norbornene compound [I] (i.e., mixture ofthe compound [I] and the compound [I-a]) may also be used, as describedlater.

Thus, when the substance containing the chain polyene group-containingnorbornene compound [I-a] as the by-product in addition to the chainpolyene group-containing norbornene compound [I] (mixture of thecompound [I] and the compound [I-a]) is used as the chain polyenegroup-containing compound (iii) of [A] in the reaction with ethylene (i)and the α-olefin of 3 to 20 carbon atoms (ii), the resulting unsaturatedethylene copolymer contains the constituent units [II-a] derived fromthe norbornene compound [I-a] in addition to the constituent units [II]derived from the norbornene compound [I], as the constituent unitsderived from the chain polyene group-containing compound.

For example, when an EMHN-containing substance, which contains a smallamount of a by-product [I-a](5-[3,7-dimethyl-2,6-octadienyl]-2-norbornene) in addition to EMHN(5-(2-ethylidene-6-methyl-5-heptenyl)-2-norbornene), is used as thechain polyene group-containing norbornene compound [I], there can beobtained a product containing the following constituent unit [II']derived from EMHN: ##STR18## and the aforesaid amount (small amount) ofthe following constituent unit [II-a'] derived from the by-product[I-a]: ##STR19##

The chain polyene group-containing norbornene compound represented bythe formula [I-a] can also be obtained by the process described inJapanese Patent Application No. 75288/1995 (filing date: Mar. 31, 1995).

That is, when cyclopentadiene is reacted with a chain non-conjugatedtriene compound represented by the following formula (a): ##STR20##wherein, m and n are each independently an integer of 1 to 5, and R¹,R², R³, R^(a) and R^(b) are each hydrogen or an alkyl group of 1 to 5carbon atoms similarly to the case of the formula [I], provided that R¹,R² and R³ do not represent hydrogen at the same time,

there can be obtained a chain polyene group-containing norbornenecompound represented by the following formula (b): ##STR21## wherein, m,n, R¹, R², R³, R^(a) and R^(b) have the same meanings as in the formula(a).

Next, the unsaturated ethylene copolymer of the invention containing theconstituent units [II] derived from the chain polyene group-containingnorbornene compound [I] and the process for preparing the copolymer aredescribed.

Unsaturated Ethylene Copolymer

The unsaturated ethylene copolymer according to the invention is [A] arandom copolymer of:

(i) ethylene,

(ii) an α-olefin of 3 to 20 carbon atoms, and

(iii) the chain polyene group-containing norbornene compound [I].

The unsaturated ethylene copolymer of the invention may be [A] a randomcopolymer of (i) ethylene, (ii) an α-olefin of 3 to 20 carbon atoms, and(iii) the chain polyene group-containing norbornene compound [I] and thechain polyene group-containing norbornene compound [I-a] in a smalleramount than that of the chain polyene group-containing norbornenecompound [I].

Examples of the α-olefins (ii) of 3 to 20 carbon atoms includepropylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene,3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene,4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene,4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene,1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene. Preferablyused are propylene, 1-butene, 1-hexene and 1-octene. These α-olefins areused singly or in combination of two or more kinds.

As described above, the chain polyene group-containing norbornenecompound [I] of the component (iii) is represented by the followingformula [I]. ##STR22##

In the formula [I], n is an integer of 1 to 5, R¹ is an alkyl group of 1to 5 carbon atoms, and R² and R³ are each independently a hydrogen atomor an alkyl group of 1 to 5 carbon atoms. The numerals 1 to 7, n+3, etc.indicate carbon numbers (positions of substituents).

Examples of the alkyl groups of 1 to 5 carbon atoms include methyl,ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl,n-pentyl and i-pentyl.

Examples of the chain polyene group-containing norbornene compounds(iii) (chain polyene group-containing norbornene compound [I]represented by the formula [I] include the above-mentioned compounds (1)to (24). Preferably used are the compounds (5), (6), (9), (11), (14),(19) and (20).

These compounds are used singly or in combination of two or more kinds.

The chain polyene group-containing norbornene compound [I] used in theinvention may be one kind of a stereoisomer, e.g., a trans form alone ora cis form alone, or it may be a mixture of stereoisomers, e.g., mixtureof a trans form and a cis form.

In the unsaturated ethylene copolymer of the invention, the constituentsunits derived from each of the monomers of (i) ethylene, (ii) theα-olefin and (iii) the chain polyene group-containing norbornenecompound (compound [I]) are arranged at random and bonded to each other,and the copolymer has a branched structure attributed to the chainpolyene group-containing norbornene compound (iii). Moreover, the mainchain of the copolymer is substantially linear. The substantially linearand crosslinked gel-free structure of the copolymer can be confirmed bythe fact that this copolymer is soluble in organic solvents and does notsubstantially contain insoluble components. For example, it can beconfirmed by the fact that the copolymer is perfectly dissolved inDecalin at 135° C. in measuring the intrinsic viscosity [η].

The unsaturated ethylene copolymer of the invention contains:

(i) constituent units derived from the ethylene in an amount of 30 to92% by mol, preferably 40 to 90% by mol, more preferably 45 to 90% bymol,

(ii) constituent units derived from the α-olefin of 3 to 20 carbon atomsin an amount of 6 to 70% by mol, preferably 8 to 60% by mol, morepreferably 10 to 55% by mol, and

(iii) constituent units derived from the chain polyene group-containingnorbornene compound [I] in an amount of 0.1 to 30% by mol, preferably0.1 to 20% by mol, more preferably 0.2 to 10% by mol.

In particular, in the unsaturated ethylene copolymer of the invention,the constituent units (i) derived from ethylene and the constituentunits (ii) derived from the α-olefin of 3 to 20 carbon atoms are presentin a molar ratio ((i) ethylene/(ii) α-olefin) of 40/60 to 92/8,preferably 45/55 to 90/10, more preferably 50/50 to 88/12.

In the unsaturated ethylene copolymer of the invention, the constituentunit derived from the chain polyene group-containing norbornene compound[I] has a structure substantially represented by the following formula[II]: ##STR23## wherein n is an integer of 1 to 5, R¹ is an alkyl groupof 1 to 5 carbon atoms, and R² and R³ are each independently a hydrogenatom or an alkyl group of 1 to 5 carbon atoms.

The structure of this constituent unit derived from the chain polyenegroup-containing norbornene compound can be confirmed by measuring a ¹³C-NMR spectrum of the copolymer.

The unsaturated ethylene copolymer of the invention has an intrinsicviscosity [η], as measured in Decalin at 135° C., of 0.05 to 10 dl/g,preferably 0.1 to 7 dl/g, more preferably 0.2 to 5 dl/g.

In addition to the chain polyene group-containing norbornene compound[I], at least one chain polyene group-containing norbornene compound[I-a] represented by the following formula [I-a] may be contained as thecomponent (iii) of [A] in the unsaturated ethylene copolymer of theinvention, in a smaller amount than that of the compound [I], preferablyin an amount of less than 50% by mol, more preferably not more than 40%by mol, particularly preferably 35% by mol, based on 100% by mol of thecompound [I] and [I-a]. ##STR24##

In the formula [I-a], n, R¹, R² and R³ have the same meanings as in theformula [I].

The chain polyene group-containing norbornene compound [I-a] is obtainedas a by-product during, for example, a process for synthesizing thechain polyene group-containing norbornene compound [I].

Such a random copolymer as mentioned above has the property [B] (iii):the total amount ([II]+[II-a]) of the constituent units [II] derivedfrom the chain polyene group-containing norbornene compound representedby the formula [I] and the constituent units [II-a] derived from thechain polyene group-containing norbornene compound represented by theformula [I-a] is in the same range as in the case of the constituentunits [II] derived from the chain polyene group-containing norbornenecompound alone. That is, [II]+[II-a] is equal to 0.1 to 30% by mol,preferably 0.1 to 20% by mol, more preferably 0.2 to 10% by mol.

The copolymerization ratio between the constituent units [II] and theconstituent units [II-a] corresponds to the molar ratio between thechain polyene group-containing norbornene compounds [I] and [I-a]. Inother words, in the total (100% by mol) of the constituent units [II]and the constituent units [II-a], the constituent units [II-a] arecopolymerized in an amount of less than 50% by mol, preferably not morethan 40% by mol, more preferably not more than 35% by mol.

This random copolymer has the property [C]: the constituent unit derivedfrom the chain polyene group-containing norbornene compound representedby the formula [I] has a structure represented by the formula [II] asdescribed above, and the constituent unit derived from the chain polyenegroup-containing norbornene compound represented by the formula [I-a]has a structure represented by the following formula [II-a]: ##STR25##wherein n, R¹, R² and R³ have the same meanings as in the formula [II].

Other properties of the copolymer (e.g., (i) amounts of ethyleneconstituent units (% by mol), (ii) ethylene constituent unit/α-olefinconstituent unit (molar ratio), intrinsic viscosity of copolymer, etc.)are the same as those in the copolymer not containing the constituentunit [II-a].

The term "chain polyene group-containing norborene compound" used hereinmeans both of the chain polyene group-containing norbornene compound [I]and the chain polyene group-containing norbornene compound [I-a], andthe term "constituent unit derived from the chain polyenegroup-containing norbornene compound" used herein means both of theconstituent unit [II] derived from the chain polyene group-containingnorbornene compound [I] and the constituent unit [II-a] derived from thechain polyene group-containing norbornene compound [I-a], unless use ofthese terms does not depart from the objects of the invention.

The unsaturated ethylene copolymer of the invention is excellent inweathering resistance, heat resistance and ozone resistance and has ahigh vulcanizing rate.

The unsaturated ethylene copolymer of the invention may be used in theunvulcanized state or may be used after vulcanized by thelater-described vulcanization process. If the copolymer is used aftervulcanized, its properties are conspicuously exhibited.

The unsaturated ethylene copolymer is particularly preferably used as aresin modifier or for preparing various rubber products.

For example, when the unsaturated ethylene copolymer is added topolypropylene, polyethylene, polybutene, polystyrene, etc. as a resinmodifier, their impact resistance and stress crack resistance areprominently improved.

The unsaturated ethylene copolymer of the invention may be vulcanizedalone or co-vulcanized with other rubber materials.

Because of its high vulcanizing rate, the unsaturated ethylene copolymercan be vulcanized for a shorter period of time or at a lower temperatureas compared with the conventional unsaturated ethylene copolymers, evenif a large amount of a vulcanizing agent is rot used. Therefore,vulcanized rubbers can be produced with high productivity.

The unsaturated ethylene copolymer of the invention is excellentparticularly in the co-vulcanizability with diene rubbers, such asnatural rubber, styrene/butadiene rubber, isoprene rubber, butadienerubber, nitrile rubber and chloroprene rubber, and the co-vulcanizatesof the unsaturated ethylene copolymer and the diene rubbers not only hasexcellent mechanical properties, abrasion resistance, dynamic fatigueresistance and oil resistance, which are inherent in the diene rubbers,but also have excellent weathering resistance, ozone resistance andthermal aging resistance.

For example, a co-vulcanizate of the unsaturated ethylene copolymer ofthe invention and natural rubber has excellent strength, weatheringresistance, ozone resistance and dynamic properties.

A co-vulcanizate of the unsaturated ethylene copolymer of the inventionand nitrile rubber has excellent weathering resistance, ozone resistanceand oil resistance.

A co-vulcanizate of the unsaturated ethylene copolymer of the inventionand butadiene rubber has excellent weathering resistance, ozoneresistance and abrasion resistance.

Preparation of Unsaturated Ethylene Copolymer

The unsaturated ethylene copolymer of the invention can be obtained bycopolymerizing (i) ethylene, (ii) the α-olefin of 3 to 20 carbon atomsand (iii) the chain polyene group-containing norbornene compound [I](and the chain polyene group-containing norbornene compound [I-a] in asmaller amount than that of the compound [I], according to necessity) inthe presence of a catalyst.

As the catalyst, catalysts comprising compounds of transition metalssuch as vanadium (V), zirconium (Zr) and titanium (Ti), andorganoaluminum compounds (organoaluminum oxy-compound) and/or an ionizedionic compound are employable, and particularly preferably used in theinvention are

(a) a catalyst comprising a soluble vanadium compound and anorganoaluminum compound, and

(b) a catalyst comprising a metallocene compound of a transition metalselected from elements of Group IVB of the periodic table and anorganoaluminum oxy-compound and/or an ionized ionic compound.

The soluble vanadium compound for forming the catalyst (a) isspecifically represented by the following formula:

    VO(OR).sub.a X.sub.b or V(OR).sub.c X.sub.d

wherein R is a hydrocarbon group, X is a halogen atom, and a, b, c, dare numbers satisfying the conditions of 0≦a≦3, 0≦b≦3, 2≦a+b≦3, 0≦c≦4,0≦d≦4 and 3≦c+d≦4.

Particular examples of the soluble vanadium compounds represented by theabove formula include VOCl₃, VO(OCH₃)Cl₂, VO(OC₂ H₅)Cl₂, VO(OC₂ H₅)₁.5Cl₁.5, VO(OC₂ H₅)₂ Cl, VO(O--n--C₃ H₇) Cl₂, VO(O--iso--C₃ H₇)Cl₂,VO(O--n--C₄ H₉)Cl₂, VO(O--iso--C₄ H₉)Cl₂, VO(O--sec--C₄ H₉)Cl₂,VO(O--t--C₄ H₉)Cl₂, VO(OC₂ H₅)₃, VOBr₂, VCl₄, VOCl₂, VO (O--n--C₄ H₉)₃,and VOCl₃.2OC₈ H₁₇ OH.

These compounds are used singly or in combination of two or more kinds.

The soluble vanadium compounds may be used in the form of electron donoraddition products of the soluble vanadium compounds which can beobtained by contacting these soluble vanadium compounds with thefollowing electron donors.

Examples of the electron donors include:

oxygen-containing electron donors, such as alcohols, phenols, ketones,aldehydes, carboxylic acids, organic acid halides, esters of organicacids or inorganic acids, ethers, diethers, acid amides, acid anhydridesand alkoxysilanes; and

nitrogen-containing electron donors, such as ammonias, amines, nitrites,pyridines and isocyanates.

More specifically, there can be mentioned:

alcohols of 1 to 18 carbon atoms, such as methanol, ethanol, propanol,butanol, pentanol, hexanol, 2-ethylhexanol, octanol, dodecanol,octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol,cumyl alcohol, isopropyl alcohol and isopropylbenzyl alcohol;

halogen-containing alcohols of 1 to 18 carbon atoms, such astrichloromethanol, trichloroethanol and trichlorohexanol;

phenols of 6 to 20 carbon atoms which may have alkyl groups, such asphenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol,cumylphenol and naphthol;

ketones of 3 to 15 carbon atoms, such as acetone, methyl ethyl ketone,methyl isobutyl ketone, acetophenone, benzophenone and benzoguinone;

aldehydes of 2 to 15 carbon atoms, such as acetaldehyde,propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde andnaphthaldehyde;

organic acid esters of 2 to 18 carbon atoms, such as methyl formate,methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octylacetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethylvalerate, methyl chloroacetate, ethyl dichloroacetate, methylmethacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methylbenzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octylbenzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyltoluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methylanisate, ethyl anisate, ethyl ethoxybenzoate, γ-butyrolactone,δ-valerolactone, coumarin, phthalide and ethyl carbonate;

acid halides of 2 to 15 carbon atoms, such as acetyl chloride, benzoylchloride, toluoyl chloride and anisoyl chloride;

ethers of 2 to 20 carbon atoms, such as methyl ether, ethyl ether,isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole anddiphenyl ether;

acid anhydrides, such as acetic anhydride, phthalic anhydride andbenzoic anhydride;

alkoxysilanes, such as ethyl silicate and diphenyldimethoxysilane;

acid amides, such as N,N-dimethylacetamide, N,N-diethylbenzamide andN,N-dimethyltoluamide;

amines, such as trimethylamine, triethylamine, tributylamine,tribenzylamine and tetramethylethylenediamine;

nitriles, such as acetonitrile, benzonitrile and tolunitrile; and

pyridines, such as pyridine, methylpyridine, ethylpyridine anddimethylpyridine.

In the preparation of the electron donor addition products of thesoluble vanadium compounds, the above electron donors may be used aloneor in combination of two or more kinds.

In the present invention, the organoaluminum compound used for formingthe catalyst (a) is represented by the following formula (III):

    R.sup.1.sub.n AlX3-n                                       (III)

wherein R¹ is a hydrocarbon group of 1 to 15, preferably 1 to 4 carbonatoms, X is a halogen atom or hydrogen, and n is 1 to 3.

The hydrocarbon group of 1 to 15 carbon atoms is, for example, an alkylgroup, a cycloalkyl group or an aryl group, and particular examplesinclude methyl, ethyl, n-propyl, isopropyl, isobutyl, pentyl, hexyl,octyl, cyclopentyl, cyclohexyl, phenyl and tolyl.

Examples of such organoaluminum compounds include:

trialkylaluminums, such as trimethylaluminum, triethylaluminum,triisopropylalumirum, triisobutylalumium, trioctylaluminum andtri-2-ethylhexylaluminum;

alkenylaluminums represented by the formula (i--C₄ H₉)_(x) Al_(y) (C₅H₁₀)_(z) (x, y and z are each a positive number, and z≧2x), such asisoprenylaluminum;

trialkenylaluminums, such as triisopropenylaluminum;

dialkylaluminum halides, such as dimethylaluminum chloride,diethylaluminum chloride, diisopropylaluminum chloride,diisobutylaluminum chloride and dimethylaluminum bromide;

alkylaluminum sesquihalides, such as methylaluminum sesquichloride,ethylaluminum sesquichloride, isopropylaluminum sesquichloride,butylaluminum sesquichloride and ethylaluminum sesquibromide;

alkylaluminum dihalides, such as methylaluminum dichloride,ethylaluminum dichloride, isopropylalumium dichloride and ethylaluminumdibromide;

dialkylaluminum hydrides, such as diethylaluminum hydride anddibutylaluminum hydride; and

alkylaluminum dihydrides, such as ethylaluminum dihydride andpropylaluminum dihydride.

Also employable as the organoaluminum compound is a compound representedby the following formula (IV):

    R.sup.1.sub.n AlY3-n                                       (IV)

wherein R¹ is the same as in the above formula (III); Y is --OR¹⁰ group,--OSiR¹¹ ₃ group, --OAlR¹² ₂ group, --NR¹³ ₂ group, --SiR¹⁴ ₃ group or--N(R¹⁵)AlR¹⁶ ₂ group; R¹⁰, R¹¹, R¹² and R¹⁶ are each methyl, ethyl,isopropyl, isobutyl, cyclohexyl or phenyl; R¹³ is hydrogen, methyl,ethyl, isopropyl, phenyl or trimethylsilyl; R¹⁴ and R¹⁵ are each methylor ethyl; and n is 1 to 2.

The organoaluminum compounds represented by the formula (IV) includecompounds of the following formulas wherein Me is methyl, Et is ethyl,Bu is butyl, and R¹ to R¹⁶ are the same as those in the formula (IV).

(1) Compounds of the formula R¹ _(n) Al(OR¹⁰)_(3-n), e.g.,dialkylaluminum alkoxides, such as dimethylaluminum methoxide,diethylaluminum ethoxide and diisobutylaluminum methoxide; partiallyalkoxylated alkylaluminums, such as ethylaluminum sesquiethoxide,butylaluminum sesquibutoxide and those having an average compositionrepresented by, e.g., R¹ ₂.5 Al(OR²)₀.5 ; and partially alkoxylated andhalogenated alkylaluminums, such as ethylaluminum ethoxychloride,butylaluminum butoxychloride and ethylaluminum ethoxybromide;

(2) Compounds of the formula R¹ _(n) Al(OSiR¹¹ ₃)_(3-n), e.g., Et₂Al(OSiMe₃), (iso-Bu)₂ Al(OSiMe₃) and (iso-Bu)₂ Al(OSiEt₃);

(3) Compounds of the formula R¹ _(n) Al(OAlR¹² ₂)_(3-n), e.g., Et₂AlOAlEt₂ and (iso-Bu)₂ AlOAl(iso-Bu)₂ ;

(4) Compounds of the formula R¹ _(n) Al(NR¹³ ₂)_(3-n), e.g., Me₂ AlNEt₂,Et₂ AlNHMe, Me₂ AlNHEt, Et₂ AlN(SiMe₃)₂ and (iso-Bu)₂ AlN(SiMe₃)₂ ;

(5) Compounds of the formula R¹ _(n) Al(SiR¹⁴ ₃)_(3-n), e.g., (iso-Bu)₂AlSiMe₃ ; and

(6) Compounds of the formula R¹ _(n) Al(N(R¹³)AlR¹⁶ ₂)_(3-n), e.g., Et₂AlN(Me)AlEt₂ and (iso-Bu)₂ AlN(Et)Al(iso-Bu)₂.

Of the above compounds, preferred are alkylaluminum halides,alkylaluminum dihalides or combinations thereof.

The organoaluminum compound used in the invention may contain anorganometallic compound component of other metal than aluminum in asmall amount.

Next, the catalyst (b) used in the invention, which comprises ametallocene compound and an organoaluminum oxy-compound or an ionizedionic compound, is described.

The metallocene compound of a transition metal selected from elements ofGroup IVB of the periodic table is represented by the following formula(V).

    ML.sub.x                                                   (V)

In the formula (V), M is a transition metal selected from elements ofGroup IVB of the periodic table, e.g., zirconium, titanium or hafnium,and x is a valence of the transition metal.

L is a ligand coordinated to the transition metal. At least one ligand Lis a ligand having a cyclopentadienyl skeleton which may have asubstituent.

Examples of the ligands having a cyclopentadienyl skeleton include alkylor cycloalkyl substituted cyclopentadienyl groups, such ascyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, n- ori-propylcyclopentadienyl, n-, i-, sec- or t-butylcyclopentadienyl,hexylcyclopentadienyl, octylcyclopentadienyl, dimethylcyclopentadienyl,trimethylcyclopentadienyl, tetramethylcyclopentadienyl,pentamethylcyclopentadienyl, methylethylcyclopentadienyl,methylpropylcyclopentadienyl, methylbutylcyclopentadienyl,methylhexylcyclopentadienyl, methylbenzylcyclopentadienyl,ethylbutylcyclopentadienyl, ethylhexylcyclopentadienyl andmethylcyclohexylcyclopentadienyl.

Further, an indenyl group, a 4,5,6,7-tetrahydroindenyl group and afluorenyl group can be also mentioned.

Those groups may be substituted with halogen atoms or trialkylsilylgroups.

Of the above ligands, particularly preferred are alkyl substitutedcyclopentadienyl groups.

When the compound represented by the formula (V) has two or more ligandsL having a cyclopentadienyl skeleton, two of the ligands having acyclopentadienyl skeleton may be bonded to each other through analkylene group such as ethylene or propylene, a substituted alkylenegroup such as isopropylidene and diphenylmethylene, a silylene group, ora substituted silylene group such as dimethylsilylene, diphenylsilyleneor methylphenylsilylene.

Examples of L other than the ligand having a cyclopentadienyl skeletoninclude a hydrocarbon group of 1 to 12 carbon atoms, an alkoxyl group,an aryloxy group, a sulfonic acid-containing group (--SO₃ R^(a)), ahalogen atom or hydrogen atom, where Ra is an alkyl group, an alkylgroup substituted with a halogen atom, an aryl group, or an aryl groupsubstituted with a halogen atom or an alkyl group.

Examples of the hydrocarbon groups of 1 to 12 carbon atoms include alkylgroups, cycloalkyl groups, aryl groups and aralkyl groups, morespecifically, there can be mentioned:

alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, sec-butyl, t-butyl, pentyl, hexyl, octyl, decyl and dodecyl;

cycloalkyl groups, such as cyclopentyl and cyclohexyl;

aryl groups, such as phenyl and tolyl; and

aralkyl group, such as benzyl and neophyl.

Examples of the alkoxy groups include methoxy, ethoxy, n-propoxy,isopropoxy, n-butoxy, isobutoxy, sec-butoxy, t-butoxy, pentoxy, hexoxyand octoxy.

The aryloxy group is, for example, phenoxy.

Examples of the sulfonic acid-containing group (--SO₃ R^(a)) includemethanesulfonato, p-toluenesulfonato, trifluoromethansulfonate andp-chlorobenzenesulfonato.

Examples of the halogen atoms include fluorine, chlorine, bromine andiodine.

The metallocene compound of the above formula wherein the valence of thetransition metal is 4 is more specifically represented by the followingformula (VI):

    R.sup.2.sub.K R.sup.3.sub.l R.sup.4.sub.m R.sup.5.sub.n M  (VI)

wherein M is the above-mentioned transition metal, R² is a group(ligand) having a cyclopentadienyl skeleton, R³, R⁴ and R⁵ are eachindependently a group having a cyclopentadienyl skeleton or the same asL other than the ligand having a cyclopentadienyl skeleton in the aboveformula (V), k is an integer of not less than 1, and k+l+m+n=4.

Listed below are examples of the metallocene compounds containingzirconium as M and containing at least two ligands having acyclopentadienyl skeleton.

Bis(cyclopentadienyl)zirconium monochloride monohydride,

Bis(cyclopentadienyl)zirconium dichloride,

Bis(cyclopentadienyl)zirconium dibromide,

Bis(cyclopentadienyl)methylzirconium monochloride,

Bis(cyclopentadienyl)zirconium phenoxymonochloride,

Bis(methylcyclopentadienyl)zirconium dichloride,

Bis(ethylcyclopentadienyl)zirconium dichloride,

Bis(n-propylcyclopentadienyl)zirconium dichloride,

Bis(isopropylcyclopentadienyl)zirconium dichloride,

Bis(t-butylcyclopentadienyl)zirconium dichloride,

Bis(n-butylcyclopentadienyl)zirconium dichloride,

Bis(sec-butylcyclopentadienyl)zirconium dichloride,

Bis(isobutylcyclopentadienyl)zirconium dichloride,

Bis(hexylcyclopentadienyl)zirconium dichloride,

Bis(octylcyclopentadienyl)zirconium dichloride,

Bis(indenyl)zirconium dichloride,

Bis(4,5,6,7-tetrahydroindenyl)zirconium dichloride,

Bis(indenyl)zirconium dibromide,

Bis(cyclopentadienyl)zirconium dimethyl,

Bis(cyclopentadienyl)zirconium methoxychloride,

Bis(cyclopentadienyl)zirconium ethoxychloride,

Bis(fluorenyl)zirconium dichloride,

Bis(cyclopentadienyl)zirconiumbis(methanesulfonato),

Bis(cyclopentadienyl)zirconiumbis(p-toluenesulfonato),

Bis(cyclopentadienyl)zirconiumbis(trifluoromethane-sulfonato),

Bis(methylcyclopentadienyl)zirconiumbis(trifluoro-methanesulfonato),

Bis(ethylcyclopentadienyl)zirconiumbis(trifluoro-methanesulfonato),

Bis(propylcyclopentadienyl)zirconiumbis(trifluoro-methanesulfonato),

Bis(butylcyclopentadienyl)zirconiumbis(trifluoro-methanesulfonato),

Bis(hexylcyclopentadienyl)zirconiumbis(trifluoro-methanesulfonato),

Bis(1,3-dimethylcyclopentadienyl)zirconium-bis(trifluoromethanesulfonato),

Bis(1-methyl-3-ethylcyclopentadienyl)zirconium-bis(trifluoromethanesulfonato),

Bis(1-methyl-3-propylcyclopentadienyl)zirconium-bis(trifluoromethanesulfonato),

Bis(1-methyl-3-butylcyclopentadienyl)zirconium-bis(trifluoromethanesulfonato),

Bis(1,3-dimethylcyclopentadienyl)zirconium dichloride,

Bis(1-methyl-3-ethylcyclopentadienyl)zirconium dichloride,

Bis(1-methyl-3-propylcyclopentadienyl)zirconium dichloride,

Bis(1-methyl-3-butylcyclopentadienyl)zirconium dichloride,

Bis(1-methyl-3-hexylcyclopentadienyl)zirconium dichloride,

Bis(1-methyl-3-octylcyclopentadienyl)zirconium dichloride,

Bis(1-ethyl-3-butylcyclopentadienyl)zirconium dichloride,

Bis(trimethylcyclopentadienyl)zirconium dichloride,

Bis(tetramethylcyclopentadienyl)zirconium dichloride,

Bis(pentamethylcyclopentadienyl)zirconium dichloride,

Bis(methylbenzylcyclopentadienyl)zirconium dichloride,

Bis(ethylhexylcyclopentadienyl)zirconium dichloride, and

Bis(methylcyclohexylcyclopentadienyl)zirconium dichloride.

Also employable in the invention are those compounds wherein the1,3-position substituted cyclopentadienyl group is replaced with a1,2-position substituted cyclopentadienyl group.

Other examples are bridge type metallocene compounds of the aboveformula (VI) wherein at least two of R², R³, R⁴ and R⁵, e.g., R² and R³,are groups (ligands) having a cyclopentadienyl skeleton, and the atleast two groups are bonded to each other through an alkylene group, asubstituted alkylene group, a silylene group or a substituted silylenegroup. In these compounds, R⁴ and R⁵ are each independently the same asL other than the ligand having a cyclopentadienyl skeleton, as describedin the formula (V).

Listed below are examples of such bridge type metallocene compounds.

Ethylenebis(indenyl)dimethylzirconium,

Ethylenebis(indenyl)zirconium dichloride,

Ethylenebis(indenyl)zirconiumbis(trifluoromethane-sulfonato),

Ethylenebis(indenyl)zirconiumbis(methanesulfonato),

Ethylenebis(indenyl)zirconiumbis(p-toluenesulfonato),

Ethylenebis(indenyl)zirconiumbis(p-chlorobenzenesulfonato),

Ethylenebis(4,5,6,7-tetrahydroindenyl)zirconium dichloride,

Isopropylidene(cyclopentadienyl-fluorenyl)zirconium dichloride,

Isopropylidene(cyclopentadienyl-methylcyclopentadienyl)zirconiumdichloride,

Dimethylsilylenebis(cyclopentadienyl)zirconium dichloride,

Dimethylsilylenebis(methylcyclopentadienyl)zirconium dichloride,

Dimethylsilylenebis(dimethylcyclopentadienyl)zirconium dichloride,

Dimethylsilylenebis(trimethylcyclopentadienyl)-zirconium dichloride,

Dimethylsilylenebis(indenyl)zirconium dichloride,

Dimethylsilylenebis(indenyl)zirconiumbis(trifluoro-methanesulfonato),

Dimethylsilylenebis(4,5,6,7-tetrahydroindenyl)zirconium dichloride,

Dimethylsilylenebis(cyclopentadienyl-fluorenyl)zirconium dichloride,

Diphenylsilylenebis(indenyl)zirconium dichloride, and

Methylphenylsilylenebis(indenyl)zirconium dichloride

Further, a metallocene compound of the following formula (A), which isdescribed in Japanese Patent Laid-Open Publication No. 268307/1992, isalso employable. ##STR26##

In the formula (A), M¹ is a metal of Group IVb, Vb or VIb of theperiodic table, e.g., titanium, zirconium or hafnium.

R¹ and R² may be the same or different, and are each hydrogen, an alkylgroup of 1 to 10, preferably 1 to 3 carbon atoms, an alkoxy group of 1to 10, preferably 1 to 3 carbon atoms, an aryl group of 6 to 10,preferably 6 to 8 carbon atoms, an aryloxy group of 6 to 10, preferably6 to 8 carbon atoms, an alkenyl group of 2 to 10, preferably 2 to 4carbon atoms, an arylalkyl group of 7 to 40, preferably 7 to 10 carbonatoms, an alkylaryl group of 7 to 40, preferably 7 to 12 carbon atoms,an arylalkenyl group of 8 to 40, preferably 8 to 12 carbon atoms, or ahalogen atom, preferably chlorine.

R³ and R⁴ may be the same or different, and are each hydrogen, a halogenatom, preferably fluorine, chlorine or bromine, an alkyl group of 1 to10, preferably 1 to 4 carbon atoms which may be halogenated, an arylgroup of 6 to 10, preferably 6 to 8 carbon atoms, or a group of --NR₂¹⁰, --SR¹⁰, --OSiR₃ ¹⁰, --SiR₃ ¹⁰ or --PR₂ ¹⁰, where R¹⁰ is a halogenatom, preferably chlorine, an alkyl group of 1 to 10, preferably 1 to 3carbon atoms, or an aryl group of 6 to 10, preferably 6 to 8 carbonatoms.

R³ and R⁴ are each particularly preferably hydrogen. R⁵ and R⁶ may bethe same or different, preferably the same, and have the same meaningsas described for R³ and R⁴ with the proviso that each of R⁵ and R⁶ isnot hydrogen. R⁵ and R⁶ are each preferably an alkyl group of 1 to 4carbon atoms which may be halogenated, for example, methyl, ethyl,propyl, isopropyl, butyl, isobutyl or trifluoromethyl, preferablymethyl. ##STR27## ═BR¹¹, ═AlR¹¹, --Ge--, --Sn--, --O--, --S--, ═SO,═SO₂, ═NR¹¹, ═CO, ═PR¹¹ or ═P(O)R¹¹, where R¹¹ R¹² and R¹³ may be thesame or different, and are each hydrogen, a halogen atom, an alkyl groupof 1 to 10, preferably 1 to 4 carbon atoms, more preferably methyl, afluoroalkyl group of 1 to 10 carbon atoms, preferably CF₃, an aryl groupof 6 to 10, preferably 6 to 8 carbon atoms, a fluoroaryl group of 6 to10 carbon atoms, preferably pentafluorophenyl, an alkoxy group of 1 to10, preferably 1 to 4 carbon atoms, particularly preferably methoxy, analkenyl group of 2 to 10, preferably 2 to 4 carbon atoms, an arylalkylgroup of 7 to 40, preferably 7 to 10 carbon atoms, an arylalkenyl groupof 8 to 40, preferably 8 to 12 carbon atoms, or an alkylaryl group of 7to 40, preferably 7 to 12 carbon atoms, or R¹¹ and R¹², or R¹¹ and R¹³may form together with the carbon atoms to which they are bonded a ring.

M² is silicon, germanium or tin, preferably silicon or germanium.

R⁷ is preferably ═CR¹¹ R₁₂, ═SiR¹¹ R¹², ═GeR¹¹ R¹², --O--, --S--, ═SO,═PR¹¹ or ═P(O)R¹¹.

R⁸ and R⁹ may be the same or different, and have the same meaning asdescribed for R¹¹.

m and n may be the same or different, and are each 0, 1 or 2, preferably0 or 1, and m+n is 0, 1 or 2, preferably 0 or 1.

Particularly preferred metallocene compounds satisfying the aboveconditions are compounds represented by the following formulas (i) to(iii). ##STR28##

In the above formulas (i), (ii) and (iii), M¹ is Zr or Hf, R¹ and R² areeach methyl or chlorine, R⁵ and R⁶ are each methyl, ethyl ortrifluoromethyl, and R⁸, R⁹, R¹⁰ and R¹² have the same meanings asdescribed above.

Of the compounds represented by the formulas (i), (ii) and (iii),particularly preferred are the following compounds:

rac-ethylene(2-methyl-1-indenyl)₂ -zirconium dichloride,

rac-dimethylsilylene (2-methyl-1-indenyl)₂ -zirconium dichloride,

rac-dimethylsilylene(2-methyl-1-indenyl)₂ -zirconium dimethyl,

rac-ethylene-(2-methyl-1-indenyl)₂ -zirconium dimethyl,

rac-phenyl(methyl)silylene-(2-methyl-1-indenyl)₂ -zirconium dichloride,

rac-diphenyl-silylene-(2-methyl-1-indenyl)₂ -zirconium dichloride,

rac-methylethylene-(2-methyl-1-indenyl)₂ -zircorium dichloride, and

rac-dimethylsilylene-(2-ethyl-1-indenyl)₂ -zirconium dichloride.

These metallocene compounds can be prepared by conventionally knownprocesses (see, for example, Japanese Patent Laid-Open Publication No.268307/1992).

In the present invention, a transition metal compound (metallocenecompound) represented by the following formula (B) is also employable.##STR29##

In the formula (B), M is a transition metal atom of Group IVa, Va or VIaof the periodic table, specifically, titanium, zirconium or hafnium.

R¹ and R² are each independently hydrogen, a halogen atom, a hydrocarbongroup of 1 to 20 carbon atoms, a halogenated hydrocarbon group of 1 to20 carbon atoms, a silicon-containing group, an oxygen-containing group,a sulfur-containing group, a nitrogen-containing group or aphosphorus-containing group.

Examples of the halogen atoms include fluorine, chlorine, bromine andiodine.

Examples of the hydrocarbon groups of 1 to 20 carbon atoms include alkylgroups, such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl,nonyl, dodecyl, eicosyl, norbornyl and adamantyl; alkenyl groups, suchas vinyl, propenyl and cyclohexenyl; arylalkyl groups, such as benzyl,phenylethyl and phenylpropyl; and aryl groups, such as phenyl, tolyl,dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl,naphthyl, methylnaphthyl, anthracenyl and phenanthryl.

Examples of the halogenated hydrocarbon groups include theabove-exemplified hydrocarbon groups which are substituted with halogenatoms.

Examples of the silicon-containing groups includemonohydrocarbon-substituted silyls, such as methylsilyl and phenylsilyl;dihydrocarbon-substituted silyls, such as dimethylsilyl anddiphenylsilyl; trihydrocarbon-substituted silyls, such astrimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl,triphenylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, tritolylsilyland trinaphthylsilyl; silyl ethers of hydrocarbon-substituted silyls,such as trimethylsilyl ether; silicon-substituted alkyl groups, such astrimethylsilylmethyl; and silicon-substituted aryl groups, such astrimethylsililphenyl.

Examples of the oxygen-containing groups include hydroxy groups; alkoxygroups, such as methoxy, ethoxy, propoxy and butoxy; aryloxy groups,such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy; andarylalkoxy groups, such as phenylmethoxy and phenylethoxy.

Examples of the sulfur-containing groups include those wherein oxygen isreplaced with sulfur in the above-exemplified oxygen-containing group.

Examples of the nitrogen-containing groups include amino group;alkylamino groups, such as methylamino, dimethylamino, diethylamino,dipropylamino, dibutylamino and dicyclohexylamino; and arylamino oralkylarylamino groups, such as phenylamino, diphenylamino, ditolylamino,dinaphthylamino and methylphenylamino.

Examples of the phosphorus-containing groups include phosphino groups,such as dimethylphosphino and diphenylphosphino.

Of these, R¹ is preferably a hydrocarbon group, particularly preferablya hydrocarbon group of 1 to 3 carbon atoms (methyl, ethyl or propyl). R²is preferably hydrogen or a hydrocarbon group, particularly preferablyhydrogen or a hydrocarbon group of 1 to 3 carbon atoms (methyl, ethyl orpropyl).

R³, R⁴, R⁵ and R⁶ are each independently hydrogen, a halogen atom, ahydrocarbon group of 1 to 20 carbon atoms or a halogenated hydrocarbongroup of 1 to 20 carbon atoms. Of these, preferred is hydrogen, thehydrocarbon group or the halogenated hydrocarbon group. At least onecombination of R³ and R⁴, R⁴ and R⁵, or R⁵ and R⁶ may form together withthe carbon atoms to which they are bonded a monocyclic aromatic ring.

When there are two or more hydrocarbon groups or halogenated hydrocarbongroups, excluding the groups for forming the aromatic ring, they may bebonded to each other to form a ring. When R⁶ is a substituent other thanthe aromatic group, it is preferably hydrogen.

Examples of the halogen atoms, the hydrocarbon groups of 1 to 20 carbonatoms and the halogenated hydrocarbon groups of 1 to 20 carbon atoms arethose described for R¹ and R².

As the ligand which contains a monocyclic aromatic ring formed by atleast one combination of R³ and R⁴, R⁴ and R⁵, or R⁵ and R⁶, asmentioned above, and is coordinated to M, there can be mentioned thefollowing ones. ##STR30##

Of these, preferred is the ligand represented by the formula (1).

The aromatic ring mentioned above may be substituted with a halogenatom, a hydrocarbon group of 1 to 20 carbon atoms or a halogenatedhydrocarbon group of 1 to 20 carbon atoms.

Examples of the halogen atoms, the hydrocarbon groups of 1 to 20 carbonatoms and the halogenated hydrocarbon groups of 1 to 20 carbon atoms forsubstituting the aromatic ring are those described for R¹ and R².

X¹ and X² are each independently hydrogen, a halogen atom, a hydrocarbongroup of 1 to 20 carbon atoms, a halogenated hydrocarbon group of 1 to20 carbon atoms, an oxygen-containing group or a sulfur-containinggroup.

Examples of the halogen atoms, the hydrocarbon groups of 1 to 20 carbonatoms, the halogenated hydrocarbon groups of 1 to 20 carbon atoms andthe oxygen-containing groups are those described for R¹ and R².

Examples of the sulfur-containing groups include those described for R¹and R² ; and further sulfonato groups, such as methylsulfonato,trifluoromethanesulfonato, phenylsulfonato, benzylsulfonato,p-toluenesulfonato, trimethylbenzenesulfonato,triisobutylbenzenesulfonato, p-chlorobenzenesulfonato andpentafluorobenzenesulfonato; and sulfinato groups, such asmethylsulfinato, phenylsulfinato, benzylsulfinato, p-toluenesulfinato,trimethylbenzenesulfinato and pentafluorobenzenesulfinato.

Y is a divalent hydrocarbon group of 1 to 20 carbon atoms, a divalenthalogenated hydrocarbon group of 1 to 20 carbon atoms, a divalentsilicon-containing group, a divalent germanium-containing group, adivalent tin-containing group, --O--, --CO--, --S--, --SO--, --SO₂ --,--NR⁷ --, --P(R⁷)--, --P(O) (R⁷)--, --BR⁷ --or --AlR⁷ --, where R⁷ ishydrogen, a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms ora halogenated hydrocarbon group of 1 to 20 carbon atoms. Examples of thedivalent hydrocarbon groups of 1 to 20carbon atoms include alkylenegroups, such as methylene, dimethylmethylene, 1,2-ethylene,dimethyl-1,2-ethylene, 1,3-trimethylene, 1,4-tetramethylene,1,2-cyclohexylene and 1,4-cyclohexylene, and arylalkylene groups, suchas diphenylmethylene and diphenyl-1,2-ethylene.

Examples of the divalent halogenated hydrocarbon groups include theabove-mentioned divalent hydrocarbon groups of 1 to 20 carbon atoms,which are halogenated, such as chloromethylene.

Examples of the divalent silicon-containing groups includealkylsilylene, alkylarylsilylene and arylsilylene groups, such asmethylsilylene, dimethylsilylene, diethylsilylene, di(n-propyl)silylene,di(i-propyl) silylene, di(cyclohexyl)silylene, methylphenylsilylene,diphenylsilylene, di(p-tolyl)silylene and di(p-chlorophenyl)silylene;and alkyldisilylene, alkylaryldisilylene and aryldisilylene groups, suchas tetramethyl-1,2-disilylene and tetraphenyl-1,2-disilylene.

Examples of the divalent germanium-containing groups include thosewherein silicon is replaced with germanium in the above-mentioneddivalent silicon-containing groups.

Examples of the divalent tin-containing groups include those whereinsilicon is replaced with tin in the above-mentioned divalentsilicon-containing groups.

R⁷ is a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms or ahalogenated hydrocarbon group of 1 to 20 carbon atoms, examples of whichare those described for R¹ and R².

Of the above groups, preferred are divalent silicon-containing groups,divalent germanium-containing groups and divalent tin-containing group,and more preferred are divalent silicon-containing groups. Of these,particularly preferred are alkylsilylene, alkylarylsilylene andarylsilylene.

Listed below are examples of the transition metal compounds representedby the formula (B).

    __________________________________________________________________________     ##STR31##                                                                    R.sup.1                                                                           R.sup.2                                                                          R.sup.5                                                                           R.sup.6                                                                          R.sup.8                                                                         R.sup.9                                                                         R.sup.10                                                                         R.sup.11                                                                          Y     X.sup.1                                                                         X.sup.2                                                                            M                                       __________________________________________________________________________    H   H  H   H  H H H  H   SiMe.sub.2                                                                          Cl                                                                              Cl   Zr                                      CH.sub.3                                                                          H  H   H  H H H  H   SiMe.sub.2                                                                          Cl                                                                              Cl   Zr                                      CH.sub.3                                                                          H  H   H  H H H  H   SiMePh                                                                              Cl                                                                              Cl   Zr                                      CH.sub.3                                                                          H  H   H  H H H  H   SiPh.sub.2                                                                          Cl                                                                              Cl   Zr                                      CH.sub.3                                                                          H  H   H  H H H  H   Si(p-tolyl).sub.2                                                                   Cl                                                                              Cl   Zr                                      CH.sub.3                                                                          H  H   H  H H H  H   Si(pClPh).sub.2                                                                     Cl                                                                              Cl   Zr                                      CH.sub.3                                                                          H  H   H  H H H  H   C.sub.2 H.sub.5                                                                     Cl                                                                              Cl   Zr                                      CH.sub.3                                                                          H  H   H  H H H  H   GeMe.sub.2                                                                          Cl                                                                              Cl   Zr                                      CH.sub.3                                                                          H  H   H  H H H  H   SnMe.sub.2                                                                          Cl                                                                              Cl   Zr                                      CH.sub.3                                                                          H  H   H  H H H  H   SiMe.sub.2                                                                          Br                                                                              Br   Zr                                      CH.sub.3                                                                          H  H   H  H H H  H   SiMe.sub.2                                                                          Cl                                                                              OSO.sub.2 CH.sub.3                                                                 Zr                                      CH.sub.3                                                                          H  H   H  H H H  H   SiMe.sub.2                                                                          Cl                                                                              SO.sub.2 CH.sub.3                                                                  Zr                                      CH.sub.3                                                                          H  H   H  H H H  H   SiMe.sub.2                                                                          Cl                                                                              Cl   Ti                                      CH.sub.3                                                                          H  H   H  H H H  H   SiMe.sub.2                                                                          Cl                                                                              Cl   Hf                                      C.sub.2 H.sub.5                                                                   H  H   H  H H H  H   SiMe.sub.2                                                                          Cl                                                                              Cl   Zr                                      nC.sub.3 H.sub.7                                                                  H  H   H  H H H  H   SiMe.sub.2                                                                          Cl                                                                              Cl   Zr                                      C.sub.6 H.sub.13                                                                  H  H   H  H H H  H   SiMe.sub.2                                                                          Cl                                                                              Cl   Zr                                      CH.sub.3                                                                          CH.sub.3                                                                         H   H  H H H  H   SiMe.sub.2                                                                          Cl                                                                              Cl   Zr                                      CH.sub.3                                                                          CH.sub.3                                                                         H   H  H H H  H   SiPh.sub.2                                                                          Cl                                                                              Cl   Zr                                      CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                                                          H  H H H  H   SiMe.sub.2                                                                          Cl                                                                              Cl   Zr                                      CH.sub.3                                                                          H  Cl  H  H H H  H   SiMe.sub.2                                                                          Cl                                                                              Cl   Zr                                      CH.sub.3                                                                          H  CH.sub.3                                                                          H  H H H  H   SiMe.sub.2                                                                          Cl                                                                              Cl   Zr                                      CH.sub.3                                                                          H  C.sub.2 H.sub.5                                                                   H  H H H  H   SiMe.sub.2                                                                          Cl                                                                              Cl   Zr                                      CH.sub.3                                                                          H  C.sub.6 H.sub.13                                                                  H  H H H  H   SiMe.sub.2                                                                          Cl                                                                              Cl   Zr                                      CH.sub.3                                                                          H  H   CH.sub.3                                                                         H H H  H   SiMe.sub.2                                                                          Cl                                                                              Cl   Zr                                      CH.sub.3                                                                          H  CH.sub.3                                                                          CH.sub.3                                                                         H H H  H   SiMe.sub.2                                                                          Cl                                                                              Cl   Zr                                      CH.sub.3                                                                          H  CH.sub.2 *.sup.1                                                                  CH.sub.3                                                                         H H H  CH.sub.2 *.sup.1                                                                  SiMe.sub.2                                                                          Cl                                                                              Cl   Zr                                      CH.sub.3                                                                          H  H   H  H H H  C.sub.6 H.sub.13                                                                  SiMe.sub.2                                                                          Cl                                                                              Cl   Zr                                      __________________________________________________________________________     *.sup.1 : R.sup.5 and R.sup.11 are bonded to each other to form a             fivemembered ring.                                                            Me: metyl; Et: ethyl; Ph: phenyl.                                             ##STR32##                                                                    R.sup.1                                                                          R.sup.2                                                                          R.sup.3                                                                           R.sup.6                                                                           R.sup.12                                                                          R.sup.13                                                                         R.sup.14                                                                         R.sup.15                                                                          Y   X.sup.1                                                                          X.sup.2                                                                         M                                        __________________________________________________________________________    H  H  H   H   H   H  H  H   SiMe.sub.2                                                                        Cl Cl                                                                              Zr                                       CH.sub.3                                                                         H  H   H   H   H  H  H   SiMe.sub.2                                                                        Cl Cl                                                                              Zr                                       CH.sub.3                                                                         H  H   H   H   H  H  H   SiPh.sub.2                                                                        Cl Cl                                                                              Zr                                       CH.sub.3                                                                         CH.sub.3                                                                         H   H   H   H  H  H   SiMe.sub.2                                                                        Cl Cl                                                                              Zr                                       CH.sub.3                                                                         H  CH.sub.3                                                                          H   H   H  H  H   SiMe.sub.2                                                                        Cl Cl                                                                              Zr                                       CH.sub.3                                                                         H  CH.sub.3                                                                          CH.sub.3                                                                          H   H  H  H   SiMe.sub.2                                                                        Cl Cl                                                                              Zr                                       CH.sub.3                                                                         H  CH.sub.2 *.sup.2                                                                  CH.sub.2 *.sup.2                                                                  CH.sub.2 *.sup.2                                                                  H  H  CH.sub.2 *.sup.2                                                                  SiMe.sub.2                                                                        Cl Cl                                                                              Zr                                       CH.sub.3                                                                         H  CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H  H  CH.sub.3                                                                          SiMe.sub.2                                                                        Cl Cl                                                                              Zr                                       __________________________________________________________________________     *.sup.2 : R.sup.3 and R.sup.12, and R.sup.6 and R.sup.15 are bonded to        each other to form a fivememebered ring, respectively.                        Me: methyl; Ph: phenyl                                                        ##STR33##                                                                    R.sup.1                                                                            R.sup.2                                                                              R.sup.3                                                                          R.sup.4                                                                              Y   X.sup.1                                                                             X.sup.2                                                                         M                                           __________________________________________________________________________    H    H      H  H      SiMe.sub.2                                                                        Cl    Cl                                                                              Zr                                          H    CH.sub.3                                                                             H  H      SiMe.sub.2                                                                        Cl    Cl                                                                              Zr                                          H    CH.sub.3                                                                             H  CH.sub.3                                                                             SiMe.sub.2                                                                        Cl    Cl                                                                              Zr                                          H    CH.sub.3                                                                             CH.sub.3                                                                         CH.sub.3                                                                             SiMe.sub.2                                                                        Cl    Cl                                                                              Zr                                          CH.sub.3                                                                           CH.sub.3                                                                             H  H      SiMe.sub.2                                                                        Cl    Cl                                                                              Zr                                          CH.sub.3                                                                           CH.sub.3                                                                             H  CH.sub.3                                                                             SiMe.sub.2                                                                        Cl    Cl                                                                              Zr                                          CH.sub.3                                                                           CH.sub.3                                                                             CH.sub.3                                                                         CH.sub.3                                                                             SiMe.sub.2                                                                        Cl    Cl                                                                              Zr                                          __________________________________________________________________________     Me: metyl.                                                               

Also employable in the invention are transition metal compounds whereinzirconium is replaced with titanium or hafnium in the above-mentionedcompounds.

The transition metal compounds mentioned above are used generally in theform of racemic modification as the olefin polymerization catalystcomponent, but they can be used also in the form of R type or S type.

The indene derivative ligands for the transition metal compounds can besynthesized in accordance with ordinary organic synthesis through, forexample, the reaction route described below. ##STR34## wherein A, B, Care each halogen.

The transition metal compounds used in the invention can be synthesizedfrom these indene derivatives in accordance with conventionally knownprocesses, for example, described in Japanese Patent Laid-OpenPublication No. 268307/1992.

In the present invention, a transition metal compound (metallocenecompound) represented by the following formula (C) is also employable.##STR35##

In the formula (C), M, R¹, R², R³, R⁴, R⁵ and R⁶ have the same meaningsdescribed for those in the aforesaid formula (B).

Of R³, R⁴, R⁵ and R⁶, at least two groups including R³ are preferablyalkyl groups, and it is more preferred that R³ and R⁵, or R³ and R⁶ arealkyl groups. These alkyl groups are preferably secondary or tertiaryalkyl groups, and may be substituted with halogen atoms orsilicon-containing groups. As the halogen atoms and thesilicon-containing groups, there can be mentioned those substituents asdescribed for R¹ and R².

Of the groups R³, R⁴, R⁵ and R⁶, other groups than the alkyl groups areeach preferably hydrogen.

Examples of the hydrocarbon groups of 1 to 20 carbon atoms includestraight chain and branched chain alkyl groups and cyclic alkyl groups,such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl,tert-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, dodecyl,eicosyl, norbornyl and adamantyl; and arylalkyl groups, such as benzyl,phenylethyl, phenylpropyl and tolylmethyl.

These groups may contain a double bond or a triple bond.

Two groups selected from R³, R⁴, R⁵ and R⁶ may be bonded to each otherto form a monocyclic or polycyclic hydrocarbon ring other than thearomatic ring.

Examples of the halogen atoms are those described for R¹ and R².

X¹, X², Y and R⁷ have the same meanings described for those in theaforesaid formula (B).

Listed below are examples of the metallocene compounds (transition metalcompounds) represented by the formula (C).

rac-Dimethylsilylene-bis(4,7-dimethyl-1-indenyl)zirconium dichloride,

rac-Dimethylsilylene-bis(2,4,7-trimethyl-1-indenyl)zirconium dichloride,

rac-Dimethylsilylene-bis(2,4,6-trimethyl-1-indenyl)zirconium dichloride,

rac-Dimethylsilylene-bis(2,5,6-trimethyl-1-indenyl)zirconium dichloride,

rac-Dimethylsilylene-bis(2,4,5,6-tetramethyl-1-indenyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(2,4,5,6,7-pentamethyl-1-indenyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(2-methyl-4-n-propyl-7-methyl-1-indenyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(4-i-propyl-7-methyl-1-indenyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(2-methyl-4-i-propyl-7-methyl-1-indenyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(2-methyl-4-i-propyl-6-methyl-1-indenyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(2-methyl-4-methyl-6-i-propyl-1-indenyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(2-methyl-4-i-propyl-5-methyl-1-indenyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(2-methyl-4,6-di(i-propyl)-1-indenyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(2-methyl-46-di(i-propyl)-7-methyl-1-indenyl)zirconium dichloride,

rac-Dimethylsilylene-bis(2-methyl-4-i-butyl-7-methyl-1-indenyl)zirconium dichloride,

rac-Dimethylsilylene-bis(2-methyl-4-sec-butyl-7-methyl-1-indenyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(2-methyl-4,6-di (sec-butyl)-1-indenyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(2-methyl-4-tert-butyl-7-methyl-1-indenyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(2-methyl-4-cyclohexyl-7-methyl-1-indenyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(2-methyl-4-benzyl-7-methyl-1-indenyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(2-methyl-4-phenylethyl-7-methyl-1-indenyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(2-methyl-4-phenyldichloromethyl-7-methyl-1-inderyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(2-methyl-4-chloromethyl-7-methyl-1-indenyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(2-methyl-4-trimethylsilylmethyl-7-methyl-1-indenyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(2-methyl-4-trimethylsiloxymethyl-7-methyl-1-indenyl)zirconiumdichloride,

rac-Diethylsilylene-bis(2-methyl-4-i-propyl-7-methyl-1-indenyl)zirconiumdichloride,

rac-Di(i-propyl)silylene-bis(2-methyl-4-i-propyl-7-methyl-i-indenyl)zirconiumdichloride,

rac-Di(n-butyl)silylene-bis(2-methyl-4-i-propyl-7-methyl-1-indenyl)zirconiumdichloride,

rac-Di(cyclohexyl)silylene-bis(2-methyl-4-i-propyl-7-methyl-1-indenyl)zirconiumdichloride,

rac-Methylphenylsilylene-bis(2-methyl-4-i-propyl-7-methyl-1-indenyl)zirconiumdichloride,

rac-Diphenylsilylene-bis(2-methyl-4-i-propyl-7-methyl-1-indenyl)zirconiumdichloride,

rac-Diphenylsilylene-bis(2-methyl-4-di(i-propyl)-1-indenyl)zirconiumdichloride,

rac-Di(p-tolyl)silylene-bis(2-methyl-4-i-propyl-7-methyl-1-indenyl)zirconiumdichloride,

rac-Di(p-chlorophenyl)silylene-bis(2-methyl-4-i-propyl-7-methyl-1-indenyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(2-methyl-4-i-propyl-7-methyl-1-indenyl)zirconium dibromide,

rac-Dimethylsilylene-bis(2-methyl-4-i-propyl-7-methyl-1-indenyl)zirconiumdimethyl,

rac-Dimethylsilylene-bis(2-methyl-4-i-propyl-7-methyl-1-indenyl)zirconiummethylchloride,

rac-Dimethylsilylene-bis(2-methyl-4-i-propyl-7-methyl-1-indenyl)zirconium-bis(methanesulfonato)

rac-Dimethylsilylene-bis(2-methyl-4-i-propyl-7-methyl-1-indenyl)zirconium-bis(p-phenylsulfinato),

rac-Dimethylsilylene-bis(2-methyl-3-methyl-4-i-propyl-6-methyl-1-indenyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(2-ethyl-4-i-propyl-6-methyl-1-indenyl)zirconiumdichloride, and

rac-Dimethylsilylene-bis(2-phenyl-4-i-propyl-6-methyl-1-indenyl)zirconiumdichloride.

Also employable in the invention are transition metal compounds whereinzirconium is replaced with titanium metal or hafnium metal in theabove-mentioned compounds.

The transition metal compounds mentioned above are used generally in theform of racemic modification, but they can be used also in the form of Rtype or S type.

The indene derivative ligands for the transition metal compounds can besynthesized in accordance with ordinary organic synthesis through, forexample, the aforementioned reaction route.

The transition metal compounds (metallocene compounds) represented bythe formula (C) can be synthesized from these indene derivatives inaccordance with conventionally known processes, for example, describedin Japanese Patent Laid-Open Publication No. 268307/1992.

In the present invention, a transition metal compound (metallocenecompound) represented by the following formula (D) is also employable.##STR36##

In the formula (D), M, R¹, X¹, X² and Y have the same meanings asdescribed for those in the aforesaid formula (B) or (C).

R¹ is preferably a hydrocarbon group, more preferably a hydrocarbongroup of 1 to 4 carbon atoms, e.g., methyl, ethyl, propyl and butyl.

X¹ and X² are each preferably a halogen atom or a hydrocarbon group of 1to 20 carbon atoms.

R² is an aryl group of 6 to 16 carbon atoms, for example, phenyl,α-naphthyl, β-naphthyl, anthracenyl, phenanthryl, pyrenyl, acenaphthyl,perinaphthenyl or aceanthrylenyl. Of these, phenyl or naphthyl ispreferred. These aryl groups may be substituted with halogen atoms,hydrocarbon groups of 1 to 20 carbon atoms or halogenated hydrocarbongroups of 1 to 20 carbon atoms such as described for R¹.

Listed below are examples of the transition metal compounds (metallocenecompounds) represented by the formula (D).

rac-Dimethylsilylene-bis(4-phenyl-1-indenyl)zirconium dichloride,

rac-Dimethylsilylene-bis(2-methyl-4-phenyl-1-indenyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(2-methyl-4-(α-naphthyl)-1-indenyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(2-methyl-4-(β-naphthyl)-1-indenyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(2-methyl-4-(1-anthracenyl)-1-indenyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(2-methyl-4-(2-anthracenyl)-1-indenyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(2-methyl-4-(9-anthracenyl)-1-indenyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(2-methyl-4-(9-phenanthryl)-1-indenyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(2-methyl-4-(p-fluorophenyl)-1-indenyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(2-methyl-4-(pentafluorophenyl)-1-indenyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(2-methyl-4-(p-chlorophenyl)-1-indenyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(2-methyl-4-(m-chlorophenyl)-1-indenyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(2-methyl-4-(p-chlorophenyl)-1-indenyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(2-methyl-4-(o,p-dichlorophenyl)phenyl-1-indenyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(2-methyl-4-(p-bromophenyl)-1-indenyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(2-methyl-4-(p-tolyl)-1-indenyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(2-methyl-4-(m-tolyl)-1-indenyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(2-methyl-4-(o-tolyl)-1-indenyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(2-methyl-4-(o,o'-dimethylphenyl)-1-indenyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(2-methyl-4-(p-ethylphenyl)-1-indenyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(2-methyl-4-(p-i-propylphenyl)-1-indenyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(2-methyl-4-(p-benzylphenyl)-1-indenyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(2-methyl-4-(p-biphenyl)-1-indenyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(2-methyl-4-(m-biphenyl)-1-indenyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(2-methyl-4-(p-trimethylsilylphenyl)-1-indenyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(2-methyl-4-(m-trimethylsilylphenyl)-1-indenyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(2-ethyl-4-phenyl-1-indenyl)zirconiumdichloride,

rac-Diphenylsilylene-bis(2-ethyl-4-phenyl-1-indenyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(2-phenyl-4-phenyl-1-indenyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(2-n-propyl-4-phenyl-1-indenyl)zirconiumdichloride,

rac-Diethylsilylene-bis(2-methyl-4-phenyl-1-indenyl)zirconiumdichloride,

rac-Di-(i-propyl)silylene-bis(2-methyl-4-phenyl-1-indenyl)zirconiumdichloride,

rac-Di-(n-butyl)silylene-bis(2-methyl-4-phenyl-1-indenyl)zirconiumdichloride,

rac-Dicyclohexylsilylene-bis(2-methyl-4-phenyl-1-indenyl)zirconiumdichloride,

rac-Methylphenylsilylene-bis(2-methyl-4-phenyl-1-indenyl)zirconiumdichloride,

rac-Diphenylsilylene-bis(2-methyl-4-phenyl-1-indenyl)zirconiumdichloride,

rac-Di(p-tolyl)silylene-bis(2-methyl-4-phenyl-1-indenyl)zirconiumdichloride,

rac-Di(p-chlorophenyl)silylene-bis(2-methyl-4-phenyl-1-indenyl)zirconiumdichloride,

rac-Methylene-bis(2-methyl-4-phenyl-1-indenyl)zirconium dichloride,

rac-Ethylene-bis(2-methyl-4-phenyl-1-indenyl)zirconium dichloride,

rac-Dimethylgermylene-bis(2-methyl-4-phenyl-1-indenyl)zirconiumdichloride,

rac-Dimethylstannylene-bis(2-methyl-4-phenyl-1-indenyl)zirconiumdichloride,

rac-Dimethylsilylene-bis(2-methyl-4-phenyl-1-indenyl)zirconiumdibromide,

rac-Dimethylsilylene-bis(2-methyl-4-phenyl-1-indenyl)zirconium dimethyl,

rac-Dimethylsilylene-bis(2-methyl-4-phenyl-1-indenyl)zirconiummethylchloride,

rac-Dimethylsilylene-bis(2-methyl-4-phenyl-1-indenyl)zirconium chlorideSO₂ Me, and

rac-Dimethylsilylene-bis(2-methyl-4-phenyl-1-indenyl)zirconium chlorideOSO₂ Me.

Also employable in the invention are transition metal compounds whereinzirconium is replaced with titanium metal or hafnium metal in theabove-mentioned compounds.

The transition metal compounds represented by the formula (D) can beprepared in accordance with "Journal of Organometallic Chem.",288(1985), pp. 63-67, and European Patent Publication No. 0,320,762(specification and examples), for example, in the following manner.##STR37## wherein Z is Cl, Br, I or o-tosyl, and H₂ R^(a) is ##STR38##

The transition metal compounds (D) are used generally in the form ofracemic modification, but they can be used also in the form of R type orS type.

In the present invention, a compound represented by the followingformula (E-1) can be also employed as the metallocene compound.

    L.sup.a MX.sub.2                                           (E- 1)

wherein, M is a metal of Group IV of the periodic table or a metal oflanthanide series;

L^(a) is a derivative of delocalization π bond group and impartsrestraint geometrical shape to the metal M active site; and

the X's are each independently hydrogen, halogen, a hydrocarbon group of20 or less carbon, silicon or germanium atoms, a silyl group or a germylgroup.

Of the compounds of the formula (E-1), preferred are compoundsrepresented by the following formula (E-2). ##STR39## wherein M istitanium, zirconium or hafnium; X is the same as described above;

Cp is a substituted cyclopentadienyl group which is π-bonded to M andhas a substituent Z;

Z is oxygen, sulfur, boron or an element of Group IVA of the periodictable;

Y is a ligand containing nitrogen, phosphorus, oxygen or sulfur; and

Z and Y may together form a condensed ring.

Listed below are examples of the compounds represented by the formula(E-2).

(Dimethyl(t-butylamide)(tetramethyl-η⁵ -cyclopentadienyl)silane)titaniumdichloride,

((t-Butylamide)(tetramethyl-η⁵-cyclopentadienyl)-1,2-ethanediyl)titanium dichloride,

(Dibenzyl(t-butylamide)(tetramethyl-η5-cyclopentadienyl)silane)titaniumdichloride,

(Dimethyl(t-butylamide)(tetramethyl-η⁵-cyclopentadienyl)silane)dibenzyltitanium,

(Dimethyl(t-butylamide)(tetramethyl-η⁵-cyclopentadienyl)silane)dimethyltitanium,

((t-Butylamide) (tetramethyl-η⁵-cyclopentadienyl)-1,2-ethanediyl)dibenzyltitanium,

((Methylamide) (tetramethyl-η⁵-cyclopentadienyl)-1,2-ethanediyl)dineopentyltitanium,

((Phenylphosphide)(tetramethyl-η⁵-cyclopentadienyl)-methylene)diphenyltitanium,

(Dibenzyl(t-butylamide)(tetramethyl-η⁵-cyclopentadienyl)silane)dibenzyltitanium,

(Dimethyl (benzylamide) (η⁵ -cyclopentadienyl) silane)di(trimethylsilyl)titanium,

(Dimethyl(phenylphosphide)-(tetramethylη⁵-cyclopentadienyl)silane)dibenzyltitanium,

(Tetramethyl-η⁵ -cyclopentadienyl)-1,2-ethanediyl)dibenzyltitanium,

(2-η⁵-(Tetramethyl-cyclopentadienyl)-1-methyl-ethanolate(2-))dibenzyltitanium,

(2 -η⁵ -(Tetramethyl-cyclopentadienyl)-1-methyl-ethanolate(2-))dimethyltitanium,

(2-((4a,4b,8a,9,9a-η)-9H-fluorene-9-yl)cyclohexanolate(2-))dimethyltitanium,and

(2-((4a,4b,8a,9,9a-η)-9H-fluorene-9-yl)cyclohexanolate(2-))dibenzyltitanium.

In the present invention, the metallocene compounds mentioned above canbe used in combination of two or more kinds.

Some examples of titanium compounds are mentioned above as themetallocene compounds, but compounds wherein titanium is replaced withzirconium or hafnium in the above-mentioned titanium compounds can bealso exemplified.

Those compounds may be used alone or in combination of two or morekinds.

As the metallocene compounds (E-1) and (E-2), zirconocene compoundswhich have zirconium as the central metal atom and have at least twoligands containing a cyclopentadienyl skeleton. In the metallocenecompounds [VI], the central metal atom is preferably titanium.

The metallocene compounds may be used by diluting with hydrocarbons orhalogenated hydrocarbons.

The metallocene compounds may be used by contacting with the particulatecarrier compounds.

As the carrier compounds, there can be used inorganic carrier compoundssuch as SiO₂, Al₂ O₃, B₂ O₃, MgO, ZrO₂, CaO, TiO₂, ZnO, Zn₂ O, SnO₂, BaOand ThO; and resins such as polyethylene, polypropylene, poly-1-butene,poly-4-methyl-1-pentene and styrene-divinylbenzene copolymer. Thesecarrier compounds may be used in combination of two or more kinds.

Next, the organoaluminum oxy-compound and the ionizable ionic compoundused for forming the catalyst (b) (catalyst comprising a metallocenecompound of a transition metal selected from elements of Group IV of theperiodic table, and an organoaluminum oxy compound or an ionizable ioniccompound) are described.

The organoaluminum oxy-compound used in the invention may be eitheraluminoxane conventionally known or a benzene-insoluble organoaluminumoxy-compound.

The conventionally known aluminoxane is represented by the followingformula (1) or (2). ##STR40## wherein R is a hydrocarbon group such asmethyl, ethyl, propyl and butyl, preferably methyl or ethyl,particularly preferably methyl, and m is an integer of not less than 2,preferably an integer of 5 to 40.

This aluminoxane may be formed from mixed alkyloxyaluminum unitsconsisting of alkyloxyaluminum units represented by the formula(OAl(R¹)) and alkyloxyaluminum units represented by the formula(OAl(R²)) (in these formulas, R¹ and R² are each the same hydrocarbongroup as described for R, and R¹ and R² are different from each other).

The conventionally known aluminoxane can be prepared by, for example,the following procedures, and the aluminoxane is generally recovered inthe form of an aromatic hydrocarbon solvent solution.

(1) An organoaluminum compound such as trialkylaluminum is added to ahydrocarbon solvent suspension of compounds containing adsorbed water orsalts containing water of crystallization, e.g., magnesium chloridehydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickelsulfate hydrate and cerous chloride hydrate, so as to allow theorganoaluminum compound to react with the adsorbed water or the water ofcrystallization, and the reaction product is recovered as an aromatichydrocarbon solvent solution.

(2) Water, ice or water vapor is allowed to directly act on anorganoaluminum compound such as trialkylaluminum in a medium such asbenzene, toluene, ethyl ether or tetrahydrofuran, and the reactionproduct is recovered as an aromatic hydrocarbon solvent solution.

Of the above procedures, the procedure (1) is preferably used.

Examples of the organoaluminum compounds used for preparing the solutionof aluminoxane include the aforesaid organoaluminum compounds. Morespecifically, there can be mentioned:

trialkylaluminums, such as trimethylaluminum, triethylaluminum,tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum,triisobutylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum,tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum,tricyclohexylaluminum and tricyclooctylaluminum;

alkenylaluminums represented by the formula (i-C₄ H₉)_(x) Al_(y) (C₅H₁₀)_(z) (x, y and z are each a positive number, and z≧2x), such asisoprenylaluminum;

dialkylaluminum halides, such as dimethylaluminum chloride,diethylaluminum chloride, diethylaluminum bromide and diisobutylaluminumchloride;

dialkylaluminum hydrides, such as diethylaluminum hydride anddiisobutylaluminum hydride;

dialkylaluminum alkoxides, such as dimethylaluminum methoxide anddiethylaluminum ethoxide; and

dialkylaluminum aryloxides, such as diethylaluminum phenoxide.

Of these, preferred are trialkylaluminums.

The organoaluminum compounds mentioned above are used singly or incombination.

The benzene-insoluble organoaluminum oxy-compound used in the inventioncan be obtained by, for example, contacting the solution of aluminoxanewith water or an active hydrogen-containing compound or contacting theorganoaluminum compound with water.

In the benzene-insoluble organoaluminum oxy-compound used for theinvention, a ratio of the absorbance at about 1,260 cm⁻¹ (D₁₂₆₀) to theabsorbance at about 1,220 cm⁻¹ (D₁₂₂₀) obtained by the infraredspectroscopic analysis of the compound, (D₁₂₆₀ /D₁₂₂₀), is not more than0.09, preferably not more than 0.08, particularly preferably in therange of 0.04 to 0.07.

The benzene-insoluble organoaluminum oxy-compound is presumed to havealkyloxyaluminum units represented by the following formula: ##STR41##wherein R⁷ is a hydrocarbon group of 1 to 12 carbon atoms. Examples ofsuch hydrocarbon groups include methyl, ethyl, n-propyl, isopropyl,n-butyl, isobutyl, pentyl, hexyl, octyl, decyl, cyclohexyl andcyclooctyl. Of these, preferred are methyl and ethyl, and particularlypreferred is methyl.

This benzene-insoluble organoaluminum oxy-compound may have, in additionto the alkyloxyaluminum units represented by the above formula,oxyaluminum units represented by the following formula: ##STR42##wherein R⁸ is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxygroup of 1 to 12 carbon atoms, an aryloxy group of 6 to 20 carbon atoms,a hydroxyl group, halogen or hydrogen.

R⁸ is different from R⁷ in the aforesaid formula.

When the organoaluminum oxy-compound contains the oxyaluminum units, itis desired that the alkyloxyaluminum units are contained in an amount ofnot less than 30% by mol, preferably not less than 50% by mol,particularly preferably not less than 70% by mol.

The organoaluminum oxy-compound used in the invention may contain asmall amount of an organic compound component of other metal thanaluminum.

The ionizable ionic compound used in the present invention includesLewis acids, ionic compounds, borane compounds and carborane compounds.

The Lewis acids include, for example, a compound represented by theformula: BR₃ wherein each R is independently a phenyl group which mayhave substituents such as fluorine, methyl and trifluoromethyl, or afluorine atom.

Examples of the compounds represented by the above formula includetrifluoroboron, triphenylboron, tris(4-fluorophenyl)boron,tris(3,5-difluorophenyl)boron, tris(4-fluoromethylphenyl)boron,tris(pentafluorophenyl)boron, tris(p-tolyl)boron, tris(o-tolyl)boron andtris (3,5-dimethylphenyl)boron.

Examples of the ionic compounds include trialkyl-substituted ammoniumsalts, N,N-dialkylanilinium salts, dialkylammonium salts andtriarylphosphonium salts.

Particular examples of the trialkyl-substituted ammonium salts include:

triethylammoniumtetra(phenyl)boron,

tripropylammoniumtetra(phenyl)boron,

tri(n-butyl)ammoniumtetra(phenyl)boron,

trimethylammoniumtetra(p-tolyl)boron,

trimethylammoniumtetra(o-tolyl)boron,

tributylammoniumtetra(pentafluorophenyl)boron,

tripropylammoniumtetra(o,p-dimethylphenyl)boron,

tributylammoniumtetra(m,m-dimethylphenyl)boron,

tributylammoniumtetra(p-trifluoromethylphenyl)boron, and

tri(n-butyl)ammoniumtetra(o-tolyl)boron.

Particular examples of the N,N,-dialkylanilinium salts include:

N,N-dimethylaniliniumtetra(phenyl)boron,

N,N-diethylaniliniumtetra(phenyl)boron, and

N,N-2,4,6-pentamethylaniliniumtetra(phenyl)boron.

Particular examples of the dialkylammonium salts include:

di(1-propyl)ammnoniumtetra(pentafluorophenyl)boron, and

dicyclohexylammoniumtetra(phenyl)boron.

Also employable as the ionic compound aretriphenylcarbeniumtetrakis(pentafluorophenyl)borate,N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate andferroceniumtetra(pentafluorophenyl)borate.

Further, also employable as the borane compound are the followingcompounds:

decaborane (14);

salts of anion, such as

bis(tri(n-butyl)ammonium)nonaborate,

bis(tri(n-butyl)ammonium)decaborate,

bis(tri(n-butyl)ammonium)undecaborate,

bis(tri(n-butyl)ammonium)dodecaborate,

bis(tri(n-butyl)ammonium)decachlorodecaborate, and

bis(tri(n-butyl)ammonium)dodecachlorododecaborate; and

salts of metallic borane anion, such as

tri(n-butyl)ammonium-bis(dodecahydridedodecaborate)cobaltate(III), and

bis(tri(n-butyl)ammonium)-bis(dodecahydridedodecaborate)nickelate(III).

Further, particular examples of carborane compounds include:

salts of anion, such as

4-carbanonaborane(14),

1,3-dicarbanonaborane(13),

6,9-dicarbadecaborane(14),

dodecahydride-1-phenyl-1,3-dicarbanonaborane,

dodecahydride-1-methyl-1,3-dicarbanonaborane,

undecahydride-1,3-dimethyl-1,3-dicarbanonaborane,

7,8-dicarbaundecaborane(13),

2,7-dicarbaundecaborane(13),

undecahydride-7,8-dimethyl-7,8-dicarbaundecaborane,

dodecahydride-11-methyl-2,7-dicarbaundecaborane,

tri(n-butyl)ammonium-1-carbadecaborate,

tri(n-butyl)ammonium-1-carbaundecaborate,

tri(n-butyl)ammonium-1-carbadodecaborate,

tri(n-butyl)ammonium-1-trimethylsilyl-1-carbadecaborate,

tri(n-butyl)ammoniumbromo-1-carbadodecaborate,

tri(n-butyl)ammonium-6-carbadecaborate(14),

tri(n-butyl)ammonium-6-carbadecaborate(12),

tri(n-butyl)ammonium-7-carbaundecaborate(13),

tri(n-butyl)ammonium-7,8-dicarbaundecaborate(12),

tri(n-butyl)ammonium-2,9-dicarbaundecaborate(12),

tri(n-butyl)ammoniumdodecahydride-8-methyl-7,9-dicarbaundecaborate,

tri(n-butyl)ammoniumundecahydride-8-ethyl-7,9-dicarbaundecaborate,

tri(n-butyl)ammoniumundecahydride-8-butyl-7,9-dicarbaundecaborate,

tri(n-butyl)ammoniumundecahydride-8-allyl-7,9-dicarbaundecaborate,

tri(n-butyl)ammoniumundecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate,and

tri(n-butyl)ammoniumundecahydride-4,6-dibromo-7-carbaundecaborate; and

salts of metallic carborane anion, such as:

tri(n-butyl)ammoniumbis(nonahydride-1,3-dicarbanonaborate)cobaltate(III),

tri(n-butyl)ammoniumbis(undecahydride-7,8-dicarbaundecaborate)ferrate(III),

tri(n-butyl)ammoniumbis(undecahydride-7,8-dicarbaundecaborate)cobaltate(III),

tri(n-butyl)ammoniumbis(undecahydride-7,8-dicarbaundecaborate)nickelate(III),

tri(n-butyl)ammnoniumbis(undecahydride-7,8-dicarbaundecaborate)cuprate(III)

tri(n-butyl)ammoniumbis(undecahydride-7,8-dicarbaundecaborate)aurate(III),

tri(n-butyl)ammoniumbis(nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate)ferrate(III),

tri(n-butyl)ammoniumbis(nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate)chromate(III),

tri(n-butyl)ammoniumbis(tribromooctahydride-7,8-dicarbaundecaborate)cobaltate(III),

tris(tri(n-butyl)ammonium)bis(undecahydride-7-carbaundecaborate)chromate(III),

bis(tri(n-butyl)ammonium)bis(undecahydride-7-carbaundecaborate)manganate(IV),

bis(tri(n-butyl)ammonium)bis(undecahydride-7-carbaundecaborate)cobaltate(III),and

bis(tri(n-butyl)ammonium)bis(undecahydride-7-carbaundecaborate)nickelate(IV).

The ionizable ionic compounds mentioned above may be used in combinationof two or more kinds.

In the present invention, the organoaluminum oxy-compound or theionizable ionic compound may be used by supporting it on theaforementioned carrier compound.

For preparing the catalyst (b), the aforementioned organoaluminumcompound may be used together with the organoaluminum oxy-compound orthe ionizable ionic compound.

In the present invention, the ethylene (i), the α-olefin (ii) and thechain polyene group-containing norbornene compound (iii) arecopolymerized in the presence of a catalyst [a] (catalyst comprising asoluble vanadium compound and a organoaluminum compound) or a catalyst[b] (catalyst comprising a metallocene compound of a transition metalselected from Group IV of the periodic table and an organoaluminumoxy-compound or an ionizable ionic compound), usually in a liquid phase.In this case, a hydrocarbon solvent is generally used, but an α-olefinsuch as propylene may be used as a solvent.

Examples of such hydrocarbon solvents include

aliphatic hydrocarbons, such as pentane, hexane, heptane, octane,decane, dodecane and kerosine, and halogenated derivatives of thesealiphatic hydrocarbons;

alicyclic hydrocarbons, such as cyclohexane, methylcyclopentane andmethylcyclohexane, and halogenated derivatives of these alicyclichydrocarbons; and

aromatic hydrocarbons, such as benzene, toluene and xylene, andhalogenated derivatives of these hydrocarbons, such as chlorobenzene.These solvents may be used in combination.

The copolymerization of ethylene (i), the α-olefin (ii) and the chainpolyene group-containing norbornene compound (iii) may be carried out byany of batchwise and continuous processes. When the copolymerization iscarried out continuously, the catalyst is used in the followingconcentration.

If the catalyst (a), i.e., catalyst comprising the soluble vanadiumcompound and the organoaluminum compound, is used in the invention, theconcentration of the soluble vanadium compound in the polymerizationsystem is in the range of usually 0.01 to 5 mmol/liter-polymerizationvolume, preferably 0.05 to 3 mmol/liter. The soluble vanadium compoundis desirably fed as a solution in a concentration of not more than 10times, preferably 1 to 7 times, more preferably 1 to 5 times, as much asthe concentration of the soluble vanadium compound present in thepolymerization system. The organoaluminum compound is fed in a molarratio of the aluminum atom to the vanadium atom (Al/V) in thepolymerization system of not less than 2, preferably 2 to 50, morepreferably 3 to 20.

The soluble vanadium compound and the organoaluminum compound [a] aregenerally fed after diluted with the aforesaid hydrocarbon solventsand/or the α-olefin (ii) in a liquid state and the chain polyenegroup-containing norbornene compound (iii) in a liquid state.

In this case, the soluble vanadium compound is desirably diluted in theabove-mentioned concentration, and the organoaluminum compound isdesirably fed after controlling the concentration to an optionalconcentration of not more than 50 times as much as the concentration ofthe organoaluminum compound in the polymerization system.

If the catalyst (b), i.e., catalyst comprising the metallocene compoundand the organoaluminum oxy-compound or the ionizable ionic compound(also referred to as "ionic ionizable compound" or "ionic compound"), isused, the concentration of the metallocene compound in thepolymerization system is in the range of usually 0.00005 to 0.1mmol/liter-polymerization volume, preferably 0.0001 to 0.05 mmol/liter.The organoaluminum oxy-compound is fed in a molar ratio of the aluminumatom to the transition metal of the metallocene compound (Al/transitionmetal) in the polymerization system of 1 to 10,000, preferably 10 to5,000.

In the case of using the ionizable ionic compound, this compound is fedin a molar ratio of the ionizable ionic compound to the metallocenecompound (ionizable ionic compound/metallocene compound) in thepolymerization system of 0.5 to 20, preferably 1 to 10.

In the case of using the organoaluminum compound, this compound is usedin such an amount that the concentration of the organoaluminum compoundin the system becomes usually about 0 to 5 mmol/liter-polymerizationvolume, preferably about 0 to 2 mmol/liter.

When the ethylene (i), the α-olefin (ii) and the chair polyenegroup-containing norbornene compound (iii) are copolymerized in thepresence of the catalyst [a] comprising the soluble vanadium compoundand the organoaluminum compound, the copolymerization reaction iscarried out under the conditions of a temperature of -50 to 100° C.,preferably -30 to 80° C., more preferably -20 to 60° C., and a pressureof more than 0 kg/cm² and not more than 50 kg/cm², preferably more than0 kg/cm² and not more than 20 kg/cm².

When the ethylene (i), the α-olefin (ii) and the chain polyenegroup-containing norbornene compound (iii) are copolymerized in thepresence of the catalyst [b] comprising the metallocene compound and theorganoaluminum oxy-compound or the ionizable ionic compound, thecopolymerization reaction is carried out under the conditions of atemperature of -20 to 150° C., preferably 0 to 120° C., more preferably0 to 100° C., and a pressure of more than 0 kg/cm² and not more than 80kg/cm², preferably more than 0 kg/cm² and not more than 50 kg/cm².

The reaction time (mean residence time in case of continuouscopolymerization process) is in the range of usually 5 minutes to 5hours, preferably 10 minutes to 3 hours, though it varies depending onthe conditions such as catalyst concentration and polymerizationtemperature.

In the present invention, the ethylene (i), the α-olefin (ii) and thechain polyene group-containing norbornene compound (iii) are fed to thepolymerization system in such amounts that the unsaturated ethylenecopolymer having the aforementioned specific composition is obtained. Inthe copolymerization, a molecular weight-modifier such as hydrogen canbe employed.

When the ethylene (i), the α-olefin (ii) and the chain polyenegroup-containing norbornene compound (iii) are copolymerized asdescribed above, the unsaturated ethylene copolymer is usually obtainedin the form of a polymerization solution containing the copolymer. Thispolymerization solution is treated in a conventional way to obtain theunsaturated ethylene copolymer.

(Vulcanizable rubber composition)

The rubber composition containing the unsaturated copolymer of ethyleneaccording to the invention is a vulcanizable rubber composition. (Therubber composition of the invention is sometimes referred to asvulcanizable rubber composition hereinafter.) This rubber compositioncan be used in the unvulcanized state, but if it is used as thevulcanized product, much more improved properties can be exhibited.

The vulcanizable rubber composition according to the invention can bevulcanized by heating it with a vulcanizing agent or irradiating it withelectron rays without using a vulcanizing agent.

The vulcanizable rubber composition of the invention may appropriatelycontain other components according to the purpose in addition to theunsaturated copolymer of ethylene, and it is desired that theunsaturated copolymer of ethylene is contained in an amount of not lessthan 20% by weight, preferably not less than 25% by weight, based on thewhole amount of the rubber composition.

Examples of the other components which may be incorporated into thecomposition include various chemicals such as reinforcing agents,inorganic fillers, softening agents, antioxidants (stabilizers),processing aids, compounds which constitute a foaming system (e.g.,foaming agent and foaming aid), plasticizers, colorants, blowing agentsand other rubber additives. The kinds and the amounts of the additivesare properly determined depending on the purpose. Of the aboveadditives, preferably used are reinforcing agent, inorganic filler,softening agent, etc. Details of these additives are described below.

Reinforcing Agent and Inorganic Filler

Examples of the reinforcing agents include carbon blacks such as SRF,GPF, FEF, MAF, HAF, ISAF, SAF, FT and MT, surface treated materialsobtained by surface treating of the above carbon blacks with silanecoupling agents, silica, activated calcium carbonate, powdery talc andpowdery silicic acid.

Examples of the inorganic fillers include precipitated calciumcarbonate, ground limestone, talc and clay.

The rubber composition of the invention may contain the reinforcingagent and/or the inorganic filler in an amount of usually not more than300 parts by weight, preferably 10 to 300 parts by weight, morepreferably 10 to 200 parts by weight, based on 100 parts by weight ofthe unsaturated copolymer of ethylene.

From the rubber composition containing the reinforcing agent in theabove-mentioned amount, a vulcanized rubber improved in mechanicalproperties such as tensile strength, tear strength and abrasionresistance can be obtained.

If the inorganic filler is added in the above-mentioned amount, thehardness can be improved without deteriorating other properties of thevulcanized rubber, and the cost can be lowered.

Softening Agent

As the softening agents, those conventionally added to rubbers can bewidely used, and examples thereof include:

petroleum type softening agents, such as process oil, lubricant,paraffin, liquid paraffin, petroleum asphalt and vaseline;

coal tar type softening agents, such as coal tar and coal tar pitch;

fatty oil type softening agents, such as castor oil, linseed oil,rapeseed oil and coconut oil;

waxes, such as tall oil, factice, beeswax, carnauba wax and lanolin;

fatty acids and fatty acid salts, such as ricinoleic acid, palmiticacid, barium stearate, calcium stearate and zinc laurate; and

synthetic high polymer materials, such as petroleum resin, atacticpolypropylene and counarone-indene resin.

Of these, preferred are petroleum type softening agents, andparticularly preferred is process oil.

The softening agent may be contained in the rubber composition of theinvention in an amount of usually not more than 200 parts by weight,preferably 10 to 200 parts by weight, more preferably 10 to 150 parts byweight, particularly preferably 10 to 100 parts by weight, based on 100parts by weight of the unsaturated ethylene copolymer.

Antioxidant

The antioxidant is preferably contained in the rubber composition of theinvention because the material life can be lengthened.

Examples of the antioxidants include:

aromatic secondary amine type stabilizers, such as phenylnaphthylamine,4,4-(α,α-dimethylbenzyl)diphenylamine, andN,N'-di-2-naphthyl-p-phenylenediamine;

phenol type stabilizers, such as 2,6-di-t-butyl-4-methylphenol, andtetrakis-(methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate)methane;

thioether type stabilizers, such asbis(2-methyl-4-(3-n-alkylthiopropionyloxy)-5-t-butylphenyl)sulfide;

benzimidazole type stabilizers, such as 2-mercaptobenzimidazole;

dithiocarbamate type stabilizers, such as nickel dibutyldithiocarbamate;and

quinoline type stabilizers, such as a polymer from2,2,4-trimethyl-1,2-dihydroquinoline. These stabilizers may be used incombination of two or more kinds.

The antioxidant may be used in an amount of not more than 5 parts byweight, preferably not more than 3 parts by weight, based on 100 partsby weight of the unsaturated copolymer of ethylene.

Processing Aid

As the processing aids, those conventionally added to rubbers can bewidely used. Examples thereof include various acids, such as ricinoleicacid, stearic acid, palmitic acid and lauric acid; salts of these higherfatty acids, such as barium stearate, zinc stearate and calciumstearate; and esters of the above acids.

The processing aid may be used in an amount of not more than 10 parts byweight, preferably not more than 5 parts by weight, based on 100 partsby weight of the unsaturated copolymer of ethylene.

Vulcanizing Agent

When the rubber composition of the invention is vulcanized by heating,compounds which constitute a vulcanization system such as vulcanizingagent, vulcanization accelerator and vulcanization aid are generallyadded to the rubber composition.

Examples of the vulcanizing agents employable herein include sulfur,sulfur compounds and organic peroxides.

There is no specific limitation on the type of sulfur, and, for example,powdery sulfur, precipitated sulfur, colloidal sulfur, surface-treatedsulfur and insoluble sulfur can be employed.

Examples of the sulfur compounds include sulfur chloride, sulfurdichloride, high-molecular weight polysulfide, morpholine disulfide,alkylphenol disulfide, tetramethylthiuram disulfide and seleniumdimethyldithiocarbamate.

Examples of the organic peroxides include:

alkyl peroxides, such as dicumyl peroxide, di-t-butyl peroxide,di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butylcumyl peroxide,di-t-amyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxine)hexyne-3, 2,S-dimethyl-2,5-di(benzoylperoxy)hexane,2,5-dimethyl-2,5-di(t-butylperoxy)hexane,α,α'-bis(t-butylperoxy-m-isopropyl)benzene and t-butyl hydroperoxide;

peroxy esters such as t-butyl peroxyacetate, t-butyl peroxyisobutyrate,t-butyl peroxybivalate, t-butylperoxymaleic acid, t-butylperoxyneodecanoate, t-butyl peroxybenzoate, and di-t-butylperoxyphthalate; and

ketone peroxides, such as dicyclohexanone peroxide. These organicperoxides may be used in combination of two or more kinds.

Of these, preferred are organic peroxides having a temperature, at whichthe half-life period thereof is one minute, of 130 to 200° C., forexample, dicumyl peroxide, di-t-butyl peroxide,di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butylcumyl peroxide,di-t-amyl peroxide and t-butyl hydroperoxide.

Of the above-mentioned various vulcanizing agents, sulfur or the sulfurcompound, especially sulfur, is preferred in the invention, becauseparticularly improved properties of the rubber composition can beexhibited.

When the vulcanizing agent is sulfur or the sulfur compound, it is usedin an amount of 0.1 to 10 parts by weight, preferably 0.5 to 5 parts byweight, based on 100 parts by weight of the unsaturated ethylenecopolymer.

When the vulcanizing agent is the organic peroxide, it is used in anamount of 0.0003 to 0.05 mol, preferably 0.001 to 0.03 mol, based on 100g of the unsaturated ethylene copolymer.

Vulcanization Accelerator

When sulfur or the sulfur compound is used as the vulcanizing agent, avulcanization accelerator is preferably used in combination.

Examples of the vulcanization accelerators include:

sulfenamide compounds, such as N-cyclohexyl-2-benzothiazole sulfenamide(CBS), N-oxydiethylene-2-benzothiazole sulfenamide andN,N-diisopropyl-2-benzothiazole sulfenamide;

thiazole compounds, such as 2-mercaptobenzothiazole (MBT),2-(2,4-dinitrophenyl)mercaptobenzothiazole,2-(2,6-diethyl-4-morpholinothio)benzothiazole and dibenzothiazyldisulfide;

guanidine compounds, such as diphenylguanidine, triphenylguanidine,diorthonitrileguanidine, orthonitrile biguanide and diphenylguanidinephthaliate;

aldehyde amines or aldehyde-ammonia compounds, such asacetaldehyde-aniline reaction product, butylaldehyde-aniline condensate,hexamethylenetetramine and acetaldehyde ammonia;

imidazoline compounds, such as 2-mercaptoimidazoline;

thiourea compounds, such as thiocarbanilide, diethylthiourea,dubutylthiourea, trimethylthiourea and diorthotolylthiourea;

thiuram compounds, such as tetramethylthiuram monosulfide,tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide,tetrabutylthiuram disulfide, pentamethylenethiuram tetrasulfide anddipentamethylenethiuram tetrasulfide (DPTT);

dithio acid salt compounds, such as zinc dimethyldithiocarbamate, zincdiethyldithiocarbamate, zinc di-n-butyldithiocarbamate, zincethylphenyldithiocabamate, zinc butylphenyldithiocarbamate, sodiumdimethyldithiocarbamate, selenium dimethyldithiocarbamate and telluriumdimethyldithiocarbamate;

xanthate compounds, such as zinc dibutylxanthate; and

zinc white.

The vulcanization accelerator is desirably used in an amount of 0.1 to20 parts by weight, preferably 0.2 to 10 parts by weight, based on 100parts by weight of the unsaturated ethylene copolymer.

Vulcanization Aid (Polyfunctional monomer)

When the organic peroxide is used as the vulcanizing agent, avulcanization aid is preferably used in an amount of 0.5 to 2 mol basedon 1 mol of the organic peroxide, preferably almost in the equimolaramount.

Examples of the vulcanization aids include:

sulfur;

quinonedioxime compounds, such as p-quinonedioxime;

(meth)acrylate compounds, such as trimethylolpropane triacrylate andpolyethylene glycol dimethacrylate;

allyl compounds, such as diallyl phthalate and triallyl cyanurate;

maleimide compounds, such as m-phenylene bismaleimide; and

divinylbenzene.

Foaming Agent

When the rubber composition of the invention contains a compound whichconstitutes a foaming system, such as a foaming agent or a foaming aid,the composition can be subjected to foam molding.

As the foaming agents, those conventionally used in the foam molding ofrubbers can be widely used. Particular examples thereof includeinorganic foaming agents, such as sodium bicarbonate, sodium carbonate,ammonium bicarbonate, ammonium carbonate and ammonium nitrite; nitrosocompounds, such as N,N'-dimethyl-N,N'-dinitrosoterephthalamide andN,N'-dinitrosopentamethylenetetramine; azo compounds, such asazodicarbonamide, azobisisobutyronitrile, azocyclohexylnitrile,azodiaminobenzene and barium azodicarboxylate; sulfonylhydrazidecompounds, such as benzenesulfonylhydrazide, toluenesulfonylhydrazide,p,p'-oxybis(benzenesulfonylhydrazide) anddiphenylsulfone-3,3'-disulfonylhydrazide; azide compounds, such ascalcium azide, 4,4-diphenyldisulfonylazide and p-toluenesulfonylazide.

Of these, preferred are nitroso compounds, azo compounds and azidecompounds.

The foaming agent may be used in an amount of 0.5 to 30 parts by weight,preferably 1 to 20 parts by weight, based on 100 parts by weight of theunsaturated copolymer of ethylene. From the rubber compositioncontaining the foaming agent in such amount, foamed products having anapparent specific gravity of 0.03 to 0.8 g/cm³ can be produced.

In combination with the foaming agent, a foaming aid can be employed.When the foaming aid is used in combination, various effects such aslowering of decomposition temperature of the foaming agent, accelerationof decomposition thereof and uniformity of the resulting foam can beexerted. Examples of the foaming agents include organic acids, such assalicylic acid, phthalic acid, stearic acid and oxalic acid, urea andits derivative.

The foaming aid may be used in an amount of 0.01 to 10 parts by weight,preferably 0.1 to 5 parts by weight, based on 100 parts by weight of theunsaturated copolymer of ethylene.

Other Rubber

The rubber composition of the invention may contain other known rubbersas long as the objects of the invention are not marred.

Examples of such rubbers include natural rubbers (NR); isoprene typerubbers, such as isoprene rubber (IR); and conjugated diene typerubbers, such as butadiene rubber (BR), styrene-butadiene rubber (SBR),acrylonitrile-butadiene rubber (NBR) and chloroprene rubber (CR).

Also employable are conventionally known ethylene-α-olefin copolymerrubbers, for example, ethylene-propylene random copolymer (EPR) andethylene-α-olefin-polyene terpolymer other than the unsaturatedcopolymer of ethylene, such as EPDM.

The vulcanizable rubber composition of the invention can be preparedfrom the unsaturated copolymer of ethylene and the above-mentioned othercomponents by conventional processes for preparing rubber blends. Forexample, the unsaturated copolymer of ethylene and other components arekneaded at 80 to 170° C. for 3 to 10 minutes using an internal mixersuch as Banbury mixer, kneader and intermixer, then the vulcanizingagent and the vulcanization accelerator or the vulcanization aid areadded if necessary, and the resulting mixture is kneaded at a rolltemperature of 40 to 80° C. for 5 to 30 minutes using a roll (e.g., anopen roll) or a kneader, followed by delivering. Thus, a rubbercomposition (rubber blend) in the form of usually ribbon or sheet can beobtained. If the temperature for kneading by the use of the internalmixer is low, the vulcanizing agent, the vulcanization accelerator andthe foaming agent may be simultaneously kneaded.

(Vulcanized rubber)

A vulcanizate (vulcanized rubber) of the rubber composition of theinvention can be obtained by generally preforming the unvulcanizedrubber composition into a desired shape using various means such as anextrusion molding machine, a calender roll, a press, an injectionmolding machine and a transfer molding machine, and simultaneously orthereafter heating the preform in a vulcanizing bath or irradiating itwith electron rays so as to vulcanize it.

When the rubber composition is vulcanized by heating, the rubbercomposition is preferably heated at a temperature of 150 to 270° C. for1 to 30 minutes using a heating bath of hot air, glass bead fluidizedbed, UHF (ultrahigh frequency electromagnetic wave), steam or LCM(molten salt bath).

When the rubber composition is vulcanized by irradiation with electronrays without using a vulcanizing agent, the preformed rubber compositionis irradiated with electron rays having energy of 0.1 to 10 MeV,preferably 0.3 to 2 MeV at an absorbed dose of 0.5 to 35 Mrad,preferably 0.5 to 10 Mrad.

In the preforming and vulcanization, a mold may be used or may not beused.

If a mold is not used, forming and vulcanization of the rubbercomposition are generally carried out continuously.

The rubber composition thus formed and vulcanized can be used forautomotive industrial parts such as weatherstrip, door glass runchannel, window frame, radiator hose, brake parts and wiper blade;industrial rubber parts such as rubber roll, belt, packing and hose;electrical insulating materials such as anode cap and grommet; civilengineering and building materials such as building gasket and civilengineering sheet; and rubberized fabrics.

The vulcanized foamed product obtained by foaming the rubber blendcontaining the foaming agent under heating can be used for heatinsulating materials, cushioning materials, sealing materials, etc.

EFFECT OF THE INVENTION

According to the invention, a chain polyene group-containing norbornenecompound suitably used for preparing a novel unsaturated ethylenecopolymer being excellent in weathering resistance, heat resistance andozone resistance and having a high vulcanizing rate can be obtained.According to the invention, further, an unsaturated ethylene copolymerhaving good balance of the above-mentioned properties can be obtained.

EXAMPLE

The present invention will be further described with reference to thefollowing examples, but it should be construed that the invention is inno way limited to those examples.

(1) In the following examples to prepare polymers, a substance(EMHN-containing substance), which contains, for example, not only EMHN(5-(2-ethylidene-6-methyl-5-heptenyl)-2-norbornene) (true EMHN) obtainedby the following examples to synthesize monomers but also a small amountof a by-product (5-[3,7-dimethyl-2,6-octadienyl]-2-norbornene), is usedas EMHN. Therefore, the term "EMHN"sometimes means a mixture(EMHN-containing substance) of the true EMHN and the by-product, and theterm "ethylene/propylene/EMHN copolymer" sometimes means a copolymercontaining true EMHN units and units derived from the by-product(EMHN-containing units) as the EMHN units, unless use of these termsdoes not depart from the objects of the invention.

(2) The proportions of the constituent units [II] derived from EMHN (I)as the main component and the constituent units [II-a] derived from theby-product [I-a] were determined in the following way.

Measuring Device and Measuring Conditions

Device

NMR: GSH-270 model, FT-NMR, manufactured by Japan Electron OpticsLaboratory Co., Ltd.

Main conditions of ¹ H-NMR spectrum measurement

Observation range: 5,400 Hz (20 ppm)

Pulse width: 7.3 μsec (45°)

Solvent: hexachlorobutadiene

Rock solvent: deuterated benzene

Measuring mode: proton non-decoupling

Measuring temperature: 120° C.

Concentration: 50 mg/0.4 cc

Number of integrating times: 1,000 to 3,000

Calculation

The area of 5.07 to 5.17 ppm region is taken as S1.

The area of 5.17 to 5.35 ppm region is taken as S2.

The proportion (% by mol) of the constituent units [II] derived from thecompound [I] as the main component and the proportion (% by mol) of theconstituent units [II-a] derived from the by-product [I-a] arecalculated by the following equations.

[I]: [S2×2/(S1+S2)]×100

[II-a]: [(S1-S2)/(S1+S2)]×100 ##STR43##

Reference Example 1 Preparation of Catalyst

A 50-ml flask equipped with a stirrer was charged with 43 mg (0.33 mmol)of anhydrous cobalt(II) chloride, 263 rg (0.66 mmol) of1,2-bis(diphenylphosphino)ethane and 23 ml of anhydrous decane in anargon atmosphere, and they were stirred at 25° C. for 2 hours. Then, 17ml of a triethylaluminum/toluene solution (concentration: 1 mol/liter,triethylaluminum: 17 mmol) was added, and the mixture was stirred at theabove temperature (25° C.) for 2 hours to prepare a catalyst.

Synthesis of 4-ethylidene-8-methyl-1,7-nonadiene (EMN)

EMN represented by the following formula was synthesized in the mannerdescribed below. ##STR44##

Into a 300-ml stainless steel (SUS316) autoclave 100 g (734 mmol) of7-methyl-3-methylene-1,6-octadiene (β-myrcene) and the total amount ofthe above-prepared catalyst were introduced in an argon atmosphere, andthe autoclave was sealed.

Then, an ethylene bomb was connected (directly) to the autoclave, andethylene was fed to the autoclave until the internal pressure of theautoclave became 35 kg/cm².

Then, the autoclave was heated to 95° C. to perform reaction. During thereaction, ethylene was intermittently added to the autoclave five timesto make up for the consumed ethylene to thereby run the reaction for 15hours in total.

After the reaction was completed, the autoclave was cooled and thenreleased. The resulting reaction mixture was poured into 100 ml of waterto separate it into an organic phase and an aqueous phase.

The organic phase thus separated was withdrawn, distilled by anevaporator to remove low-boiling substances and then subjected to20-plate precision vacuum distillation, to obtain 83 g of the desiredEMN (yield: 69%, β-myrcene conversion ratio: 90%).

Additionally, 16 g of 5,9-dimethyl-1,4,8-decatriene (yield: 13%) wasproduced as a by-product.

The results of analysis of the 4-ethylidene-8-methyl-1,7-nonadiene (EMN)obtained above are as follows.

(1) Boiling point: 103 to 105° C./30 mmHg

(2) GC-MS (gas chromatography mass spectrometry):

m/z 164 (M⁺ molecule ion peak),

149, 123, 95, 69, 41, 27

Measuring Conditions of Gas Chromatography

Column: capillary column DB-1701 (0.25 mm×30 m), available from J & WScientific Co.

Vaporization temperature: 250° C.

Column temperature: maintained at 60° C. for 5 min, then raised up to200° C. at 10° C./min

(3) Infrared absorption spectrum (neat, cm⁻¹) absorption peaks: 3080,2975, 2925, 2850, 1670, 1640, 1440, 1380, 1235, 1110, 995, 910, 830

(4) ¹ H-NMR spectrum (solvent: CDCl₃)

The absorption peaks are described below.

                  TABLE 1                                                         ______________________________________                                        ppm (δ)    Proton number, Peak                                          ______________________________________                                        1.59             (3H, doublet, J = 7 Hz)                                      1.60             (3H, singlet)                                                1.68             (3H, singlet)                                                2.00             (2H, multiplet)                                              2.06             (2H, multiplet)                                              2.80             (2H, doublet, J = 7 Hz)                                      4.9-5.2          (3H, multiplet)                                              5.30             (1H, quartet, J = 7 Hz)                                      5.75             (1H, multiplet)                                              ______________________________________                                    

Example 1 Synthesis of 5-(2-ethylidene-6-methyl-5-heptenyl)-2-norbornene(EMHN, chain polyene group-containing norbornere compound (11)exemplified above)

Into a 1-liter stainless steel autoclave, 240.7 g (1.156 mol) of4-ethylidene-8-methyl-1,7-nonadiene (EMN) obtained in Reference Example1 was introduced. Then, to the autoclave was introduced 153.0 g (2.314mol) of cyclopentadiene over a period of 5 hours, with stirring EMNunder heating at 190° C. and a nitrogen pressure of 2 kg/cm².

The system was then heated at 190° C. for 1 hour with stirring andcooled to room temperature, followed by releasing the autoclave.

The reaction mixture thus obtained was subjected to vacuum distillationto remove low-boiling substances, and the residue was subjected to40-plate precision vacuum distillation to obtain 53.8 g of the desiredEMHN (5-(2-ethylidene-6-methyl-5-heptenyl)-2-norbornene). The yield was20.2% on the basis of 4-ethylidene-8-methyl-1,7-nonadiene.

Additionally, 10.1 g of [5-(3,7-dimethyl-2,6-octadienyl)]-2-norbornenewas obtained as a by-product. Therefore, the ratio of EMHN to theby-product was 5.33/1.

The physiochemical data of the EMHN are as follows.

(1) Boiling point: 138° C./3 mmHg

(2) Gas chromatography mass spectrometry:

m/z 230 (M⁺), 215, 187, 123, 91, 69

Measuring Conditions of Gas Chromatography

Column: capillary column DB-1701 (0.25 mm×30 m), available from J & WScientific Co.

Vaporization temperature: 250° C.

Column temperature: maintained at 40° C. for 5 min, then raised up to200° C. at 5° C./min

(3) Infrared absorption spectrum (neat, cm⁻¹)

3050, 2960, 2925, 2850, 1660, 1630, 1570, 1440, 1375, 1345, 1330, 1250,1220, 1100, 980, 925, 900, 820, 780, 715

(4) Proton NMR spectrum (CDCl₃ solvent)

The absorption peaks are described below.

                  TABLE 2                                                         ______________________________________                                        ppm (δ)    Proton number, Peak                                          ______________________________________                                        0.55             (1H, multiplet)                                              1.1-2.3          (10H, multiplet)                                             1.55             (3H, doublet, J = 7 Hz)                                      1.60             (3H, singlet)                                                1.67             (3H, singlet)                                                2.7              (2H, multiplet)                                              5.10             (1H, multiplet)                                              5.20             (1H, quartet, J = 7 Hz)                                      5.9-6.2          (2H, multiplet)                                              ______________________________________                                    

Example 2

Into a 1-liter stainless steel autoclave, 153.0 g (1.157 mol) ofdicyclopentadiene and 240.7 g (1.156 mol) of4-ethylidene-8-methyl-1,7-nonadiene were introduced, and they werestirred under heating at 190° C. for 6 hours under a nitrogen pressureof 2 kg/cm² to perform reaction.

After the reaction was completed, the system was cooled to roomtemperature and the autoclave was released. The reaction mixture thusobtained was subjected to vacuum distillation to remove low-boilingsubstances, and the residue was subjected to 40-plate precision vacuumdistillation to obtain 48.7 g of the desired EMHN. The yield was 18.3%on the basis of 4-ethylidene-8-methyl-1,7-nonadiene.

Additionally, 9.7 g of 5-[3,7-dimethyl-2,6-octadienyl]-2-norbornene wasobtained as a by-product. Therefore, the ratio of EMHN to the by-productwas 5.02/1.

Reference

[5-(3,7-dimethyl-2,6-octadienyl]-2-norbornene

(1) Proton NMR spectrum (CDCl₃ solvent):

0.55 (1H, multiplet)

1.0-2.3 (8H, multiplet)

1.60 (6H, singlet)

1.68 (3H, singlet)

2.7 (2H, multiplet)

5.1 (2H, multiplet)

5.9-6.2 (2H, multiplet)

(2) Infrared absorption spectrum (neat, cm⁻¹)

3050, 2960, 2925, 2860, 1670, 1640, 1450, 1380, 1340, 1250, 1105, 900,830, 720

Example 3

In a 2-liter polymerizer equipped with a stirring blade,terpolymerization reaction of ethylene, propylene and EMHN(5-(2-ethylidene-6-methyl-5-heptenyl)-2-norbornene) obtained in Example1 was continuously carried out.

This polymerization reaction was carried out in the following manner.

To the polymerizer were continuously fed, from the top thereof, a hexanesolution of the EMHN-containing substance at a feed rate of 0.5 l/hr sothat the concentration in the polymerizer became 15 mmol/l, a hexanesolution of VO(OC₂ H₅)Cl₂ as a catalyst at a feed rate of 0.5 l/hr sothat the vanadium concentration in the polymerizer became 0.2 mmol/l, ahexane solution of ethylaluminum sesquichloride (Al(C₂ H₅)₁.5 Cl₁.5) asa catalyst at a feed rate of 0.5 l/hr so that the aluminum concentrationin the polymerizer became 2.0 mmol/l, and hexane at a feed rate of 0.5l/hr. On the other hand, the polymer solution was continuously drawn outfrom the top of the polymerizer so that the polymer solution in thepolymerizer was kept constant in an amount of 1 liter.

To the polymerization system were further fed ethylene at a feed rate of140 l/hr, propylene at a feed rate of 160 l/hr and hydrogen at a feedrate of 15 l/hr using bubbling tubes. The copolymerization reaction wasconducted at 30° C. by circulating a cooling medium through a jacketprovided outside the polymerizer.

Through the copolymerization reaction under the above conditions, apolymer solution containing an ethylene/propylene/EMHN-containingsubstance copolymer was obtained.

The polymer solution thus obtained was deashed using hydrochloric acidand then introduced into a large amount of methanol to precipitate thepolymer, followed by vacuum drying at 100° C. for 24 hours.

Thus, an ethylene/propylene/EMHN-containing substance copolymer wasobtained in an amount of 68 g per hour.

In the copolymer, the ethylene constituent units were contained in anamount of 67.2% by mol, the propylene constituent units were containedin an amount of 31.6% by mol, the constituent units derived from theEMHN-containing substance were contained in an amount of 1.2% by mol,and the molar ratio of the ethylene constituent unit/propyleneconstituent unit was 68/32. The intrinsic viscosity [η] of the copolymerwas 2.5 dl/g.

The amount (1.2% by mol) of the EMHN-containing substance constituentunits were composed of 0.85% by mol of EMHN constituent units and 0.35%by mol of constituent units derived from a by-product([5-(3,7-dimethyl-2,6-octadienyl)]-2-norbornene).

Then, a composition containing 100 parts by weight of theethylene/propylene/EMHN-containing substance copolymer, 5 parts byweight of zinc white No. 1, 1 part by weight of stearic acid, 80 partsby weight of N330 (trade name: Seast 3, available from Tokai CarbonK.K.), 50 parts by weight of oil (trade name: Santhen 4240, availablefrom San Oil K.K.), 1.0 part by weight of a vulcanization accelerator A(trade name: Nocceller TT, available from Ouchi Shinko Kagaku K.K.), 0.5part by weight of a vulcanization accelerator B (trade name: NoccellerM, available from Ouchi Shinko Kagaku K.K.) and 1.5 parts by weight ofsulfur as shown in the following table was kneaded by a 6-inch open rollto obtain an unvulcanized rubber blend

(unvulcanized rubber composition).

The ingredients of the unvulcanized rubber blend are set forth in Table3.

Estimation of a vulcanizing rate (T90 (min)) of the rubber blendresulted in 6.1.

The result is set forth in Table 4.

The vulcanizing rate was determined in the following manner. As ameasuring device, JSR curelastometer 3 model (Japan Synthetic RubberCo., Ltd.) was used. A difference between the maximum value MH and theminimum value ML of the torque obtained from the vulcanization curve wastaker as ME (ME=MH-ML), and the vulcanizing rate was estimated in termsof the period of time (T90 (min)) required for the difference ME toreach 90% ME. Estimation of T90 (min) of the above rubber blend resultedin 6.1.

Subsequently, the unvulcanized rubber blend obtained by blending theingredients shown in Table 3 was press vulcanized at 160° C. for aperiod of T90 (min)+2 min (i.e., 6.8+2=8.8 (min)), and the properties ofthe resulting vulcanized rubber were measured. That is, T90 (min) of theunvulcanized rubber blend and the properties of the vulcanized rubberwere evaluated.

The vulcanized rubber had a 100% modulus (M100, kgf/cm²) of 35, a 200%modulus (M200, kgf/cm²) of 85, a 300% modulus (M300, kgf/cm²) of 125, atensile strength (T_(B), kgf/cm²) of 195, an elongation (E_(B), %) of460 and a hardness (H_(S), JIS A) of 68.

The results are set forth in Table 4.

The above properties were all measured in accordance with JIS K 6301.

                  TABLE 3                                                         ______________________________________                                        Ingredients of Unvulcanized                                                   Rubber Blend         Part(s) by weight                                        ______________________________________                                        Ethylene/propylene/EMHN copolymer                                                                  100                                                      Zinc white No. 1     5                                                        Stearic acid         1                                                        N330                 80                                                       (Seast 3, from Tokai Carbon K.K.)                                             Oil (Santhen 4240, from San Oil K.K.)                                                              50                                                       Vulcanization accelerator A                                                                        1.0                                                      (Nocceller TT, from Ouchi Shinko                                              Kagaku K.K.)                                                                  Vulcanization accelerator B                                                                        0.5                                                      (Nocceller M, from Ouchi Shinko                                               Kagaku K.K.)                                                                  Sulfur               1.5                                                      ______________________________________                                    

Example 4

Copolymerization reaction was carried out in the same manner as inExample 3 except that the EMHN-containing substance was fed so that theconcentration in the polymerizer became 5.9 mmol/l, ethylene was fed ata feed rate of 130 l/hr, and propylene was fed at a feed rate of 170l/hr, to thereby obtain an ethylene/propylene/EMHN-containing substancecopolymer in an amount of 79 g per hour.

In the copolymer thus obtained, the ethylene constituent units werecontained in an amount of 62.2% by mol, the propylene constituent unitswere contained in an amount of 37.3% by mol, the constituent unitsderived from the EMHN-containing substance were contained in an amountof 0.55% by mol, and the molar ratio of the ethylene constituentunit/propylene constituent unit was 63/37. The intrinsic viscosity [η]of the copolymer was 2.1 dl/g.

The amount (0.55% by mol) of the EMHN-containing substance constituentunits were composed of 0.38% by mol of EMHN constituent units and 0.17%by mol of constituent units derived from a by-product([5-(3,7-dimethyl-2,6-octadienyl)]-2-norbornene).

Then, an unvulcanized rubber blend was obtained in the same manner as inExample 3 except that the above-obtained copolymer was used in place ofthe ethylene/propylene/EMHN-containing substance copolymer of Example 3.

Estimation of a vulcanizing rate (T90 (min)) of the rubber blendresulted in 7.7.

The unvulcanized rubber blend was obtained in the same manner as inExample 3 except that the above-obtainedethylene/propylene/EMHN-containing substance copolymer was used. Theunvulcanized rubber blend was then press molded.

The properties of the resulting vulcanized rubber are described below.

M100: 27, M200: 70, M300: 101, tensile strength (T_(B)): 161, elongation(E_(B)): 530, hardness (H_(S)): 67

The results are set forth in Table 4.

Comparative Example 1

In a 2-liter polymerizer equipped with a stirring blade,copolymerization reaction of ethylene, propylene and5-ethylidene-2-norbornene (ENB) was continuously carried out.

In detail, to the polymerizer were continuously fed, from the topthereof, a hexane solution of ENB (7.1 g/l) at a feed rate of 0.5 l/hr,a hexane solution of VO(OC₂ H₅)Cl₂ (0.8 mmol/l) as a catalyst at a feedrate of 0.5 l/hr, a hexane solution of ethylaluminum sesquichloride(Al(C₂ H₅)₁.5 Cl₁.5) (8.0 mmol/l) as a catalyst at a feed rate of 0.5l/hr and hexane at a feed rate of 0.5 l/hr. On the other hand, thepolymer solution was continuously drawn out from the top of thepolymerizer so that the polymer solution in the polymerizer was keptconstant in an amount of 1 liter. To the polymerization system werefurther fed ethylene at a feed rate of 120 l/hr, propylene at a feedrate of 180 l/hr and hydrogen at a feed rate of 5 l/hr using bubblingtubes. The copolymerization reaction was conducted at 30° C. bycirculating a cooling medium through a jacket provided outside thepolymerizer. Through the copolymerization reaction under the aboveconditions, a polymer solution containing an ethylene/propylene/ENBcopolymer was obtained.

The polymer solution thus obtained was deashed using hydrochloric acidand then introduced into a large amount of methanol to precipitate thepolymer, followed by vacuum drying at 100° C. for 24 hours.

Thus, an ethylene/propylene/ENB copolymer was obtained in an amount of64.8 g per hour.

In the copolymer thus obtained, the ethylene constituent units werecontained in an amount of 66.8% by mol, the propylene constituent unitswere contained in an amount of 31.4% by mol, the ENB constituent unitswere contained in an amount of 1.8% by mol, and the molar ratio of theethylene constituent unit/propylene constituent unit was 68/32. Theintrinsic viscosity [η] of the copolymer was 2.2 dl/g.

Estimation of a vulcanizing rate (T90 (min)) of the rubber blendresulted in 11.2.

Further, an unvulcanized rubber blend was prepared in the same manner asin Example 3 except that the above-obtained copolymer was used, and thenpress molded.

The properties of the resulting vulcanized rubber are described below.

M100: 30, M200: 74, M300: 117, tensile strength (T_(B)): 168, elongation(E_(B)): 400, hardness (H_(S)): 68

The results are set forth in Table 4.

Example 5

Into a 2-liter stainless steel autoclave thoroughly purged withnitrogen, 900 ml of heptane and 15 ml of the EMHN-containing substanceobtained in Example 1 were introduced. Then, propylene was furtherintroduced so that the internal pressure of the system became 3.5 kg/cm²-G at 80° C.

To the system was then fed ethylene until the pressure of the systembecame 8 kg/cm² -G.

Subsequently, 1 mmol of triisobutylaluminum, 0.005 mmol oftriphenylcarbeniumtetrakis(pentafluorophenyl)borate and 0.001 mmol of[dimethyl(t-butylamide)(tetramethylcyclo-pentadienyl)silane]titaniumdichloride were pressed into the system with nitrogen to initiate thepolymerization.

Then, only ethylene was continuously fed so that the total pressure waskept at 8 kg/cm² -G, and the polymerization was continued at 80° C. for20 minutes. A small amount of ethanol was added to the system so as toterminate the polymerizatin reaction, and the unreacted monomers werepurged out.

The resulting polymer solution was introduced into a large excess ofmethanol to precipitate a polymer.

The polymer thus precipitated was recovered by filtration and mixed with30 mg of Irganox 1010 (stabilizer, available from Ciba-GeigyCorporation) and 60 mg of Mark 329k (stabilizer, available from AsahiDenka K.K.). Then, the mixture was dried at 120° C. for one night underreduced pressure.

As a result, 60.1 g of an ethylene/propylene/EMHN-containing substancecopolymer was obtained. This copolymer contained 64.9% by mol ofethylene units, 33.7% by mol of propylene units and 1.4% by mol ofEMHN-containing substance units, and had a molar ratio of the ethyleneunits to the propylene units of 65.8/34.2 (ethylene units/propyleneunits) and an intrinsic viscosity [η] of 3.01 dl/g.

The amount (1.4% by mol) of the EMHN-containing substance constituentunits were composed of 1.0% by mol of EMHN constituent units and 0.4% bymol of constituent units derived from a by-product([5-(3,7-dimethyl-2,6-octadienyl)]-2-norbornene).

Estimation of a vulcanizing rate (T90 (min)) of the rubber blendresulted in 5.4.

Further, an unvulcanized rubber blend was prepared in the same manner asin Example 3 except that the above-obtained copolymer was used, and thenpress molded.

The properties of the resulting vulcanized rubber are described below.

M100: 45, M200: 93, M300: 135, tensile strength (T_(B)): 170, elongation(E_(B)): 420, hardness (H_(S)): 69.

The results are set forth in Table 4.

Example 6

Polymerization was carried out in the same manner as in Example 5 exceptthat the amount of heptane was varied to 900 ml, 100 ml of 1-octene wasintroduced in place of propylene, and the polymerization time was variedto 15 minutes. As a result, 48 g of an ethylene/1-octene/EMHN-containingsubstance copolymer was obtained. This copolymer contained 78.6% by molof ethylene units, 19.7% by mol of 1-octene units and 1.7% by mol ofEMHN-containing substance units, and had a molar ratio of the ethyleneunits to the 1-octene units of 80.0/20.0 (ethylene units/1-octene units)and an intrinsic viscosity [η] of 2.21 dl/g.

The amount (1.7% by mol) of the EMHN-containing substance constituentunits were composed of 1.2% by mol of EMHN constituent units and 0.5% bymol of constituent units derived from a by-product([5-(3,7-dimethyl-2,6-octadienyl)]-2-norbornene).

Estimation of a vulcanizing rate (T90 (min)) of the rubber blendresulted in 5.9.

Further, an unvulcanized rubber blend was prepared in the same manner asin Example 3 except that the above-obtained copolymer was used, and thenpress molded.

The properties of the resulting vulcanized rubber are described below.

M100: 38, M200: 90, M300: 132, tensile strength (T_(B)): 150, elongation(E_(B)): 380, hardness (H_(S)): 67.

The results are set forth in Table 4.

Example 7

Polymerization was carried out in the same manner as in Example 5 exceptthat 1-butene was introduced in place of propylene so that the internalpressure of the system became 3.7 kg/cm² -G at 80° C., and thepolymerization time was varied to 30 minutes.

As a result, 54 g of an ethylene/1-butene/EMHN-containing substancecopolymer was obtained. This copolymer contained 68.0% by mol ofethylene units, 30.6% by mol of 1-butene units and 1.4% by mol ofEMHN-containing substance units, and had a molar ratio of the ethyleneunits to the 1-butene units of 69.0/31.0 (ethylene units/1-butene units)and an intrinsic viscosity [η] of 2.51 dl/g.

The amount (1.4% by mol) of the EMHN-containing substance constituentunits were composed of 0.98% by mol of EMHN constituent units and 0.42%by mol of constituent units derived from a by-product([5-(3,7-dimethyl-2,6-octadienyl)]-2-norbornene).

Estimation of a vulcanizing rate (T90 (min)) of the rubber blendresulted in 6.0.

Further, an unvulcanized rubber blend was prepared in the same manner asin Example 3 except that the above-obtained copolymer was used, and thenpress molded.

The properties of the resulting vulcanized rubber are described below.

M100: 33, M200: 82, M300: 120, tensile strength (T_(B)): 185, elongation(E_(B)): 470, hardness (H_(S)): 66.

The results are set forth in Table 4.

Example 8 Synthesis of[5-(2-ethylidene-6-methyl-5-heptenyl)]-2-norbornene (EMHN)

Into a 1-liter stainless steel autoclave, 316 g (1.83 mol) of the4-ethylidene-8-methyl-1,7-nonadiene (EMN, purity: 95%) obtained inExample 2 and 24.2 g (0.183 mol) of dicyclopentadiene (DCPD) wereintroduced, and they were reacted at 220° C. for 2 hours under anitrogen pressure of 2 kg/cm². Then, the system was cooled to roomtemperature, and the autoclave was released. The analysis of thereaction product by means of gas chromatography under the same measuringconditions as described in the Reference Example resulted in a DCPDconversion ratio of 96% and a selectivity of the desired EMHN (on thebasis of cyclopentadiene) of 57%. The reaction mixture was subjected tosimple distillation under reduced pressure to remove EMN remaining inthe reaction mixture, and the residue was subjected to 40-plateprecision vacuum distillation. Thus, an EMHN-containing substance wasobtained in an amount of 43 g, and the desired EMHN was obtained in anamount of 40.9 g (isolated yield: 48%, on the basis of cyclopentadiene).

Additionally, 2.1 g of [5-(3,7-dimethyl-2,6-octadienyl)]-2-norbornenewas obtained as a by-product. Therefore, the ratio of EMHN to theby-product was 19.5/1 (EMHN/by-product).

The physiochemical data of the EMHN are as follows.

Boiling point: 138° C./3 mmHg

Gas chromatography mass spectrometry:

m/z 230 (M⁺), 215, 187, 123, 91, 69

Measuring conditions of gas chromatography: the same as in ReferenceExample 1

Infrared absorption spectrum (neat, cm⁻¹) 3050, 2960, 2925, 2850, 1660,1630, 1570, 1440, 1375, 1345, 1330, 1250, 1220, 1100, 980, 925, 900,820, 780, 715

Proton NMR spectrum (CDCl₃ solvent, 500 MHz NMR)

0.55 (1H, multiplet)

1.1-2.3 (10H, multiplet)

1.55 (3H, doublet, J=7 Hz)

1.60 (3H, singlet)

1.67 (3H, singlet)

2.7 (2H, multiplet)

5.10 (1H, multiplet)

5.20 (1H, quartet, J=7 Hz)

5.9-6.2 (2H, multiplet)

Example 9

Copolymerization was carried out in the same marner as in Example 3except that an EMHN-containing substance having a purity of 95% wasused, to thereby obtain an ethylene/propylene/EMHN-containing substancecopolymer in an amount of 65 g per hour.

In the copolymer thus obtained, the ethylene constituent units werecontained in an amount of 67.9% by mol, the propylene constituent unitswere contained in an amount of 30.9% by mol, the EMHN-containingsubstance constituent units were contained in an amount of 1.2% by mol,and the molar ratio of the ethylene constituent unit/propyleneconstituent unit was 69/31. The intrinsic viscosity [η] of the copolymerwas 2.6 dl/g.

The amount (1.2% by mol) of the EMHN-containing substance constituentunits were composed of 1.0% by mol of EMHN constituent units and 0.2% bymol of constituent units derived from a by-product([5-(3,7-dimethyl-2,6-octadienyl)]-2-norbornene).

Then, the ethylene/propylene/EMHN-containing substance copolymer wasblended with other ingredients in the sane manner as in Example 3 toobtain a rubber blend. Estimation of a vulcanizing rate T90 (min) of therubber blend resulted in 6.2.

The unvulcanized rubber blend was prepared in the same manner as inExample 3 except that the above-obtained copolymer was used, and thenpress molded.

The properties of the resulting vulcanized rubber are described below.

M100: 36, M200: 87, M300: 128, tensile strength (T_(B)): 196, elongation(E_(B)): 470, hardness (H_(S)): 68.

The results are set forth in Table 4.

                  TABLE 4                                                         ______________________________________                                                                                     Comp                                        Ex. 3  Ex. 4  Ex. 5                                                                              Ex. 6                                                                              Ex. 7                                                                              Ex. 9                                                                              Ex. 1                            ______________________________________                                        Properties of                                                                 vulcanized rubber                                                             M.sub.100  35     27     45   38   33   36   30                               M.sub.200  85     70     93   90   82   87   74                               M.sub.300  125    101    135  132  120  128  117                              T.sub.B    195    161    170  150  185  196  168                              E.sub.B    460    530    420  380  470  470  400                              H.sub.S    68     67     69   67   66   68   68                               T.sub.90 (minute)                                                                        6.1    7.7    5.4  5.9  6.0  6.2  11.2                             ______________________________________                                         Remarks in Table 4                                                            M.sub.100 : 100% tensile modulus (kgf/cm.sup.2)                               M.sub.200 : 200% tensile modulus (kgf/cm.sup.2)                               M.sub.300 : 300% tensile modulus (kgf/cm.sup.2)                               T.sub.B : tensile strength (kgf/cm.sup.2)                                     E.sub.B : elongation (%)                                                      H.sub.S : hardness (measured in accordance with JIS A)                        T.sub.90 (min): vulcanizing rate (min) measured at 160° C.        

What is claimed is:
 1. A chain polyene group-containing norbornenecompound represented by the formula (I): ##STR45## wherein n is aninteger of 1 to 5, R¹ is a hydrogen atom or an alkyl group of 1 to 5carbon atoms, and R² and R³ are each independently a hydrogen atom or analkyl group of 1 to 5 carbon atoms, provided that R¹ and R² are nothydrogen at the same time.
 2. A process for preparing a chain polyenegroup-containing norbornene compound as claimed in claim 1, comprisingreacting cyclopentadiene with a branched chain polyene compoundrepresented by the formula: ##STR46## wherein n is an integer of 1 to 5,R¹ is an alkyl group of 1 to 5 carbon atoms, and R² and R³ are eachindependently a hydrogen atom or an alkyl group of 1 to 5 carbon atoms.3. An unsaturated ethylene copolymer wherein:(A) said copolymer is arandom copolymer of(i) ethylene, (ii) an α-olefin of 3 to 20 carbonatoms, and (iii) at least one chain polyene group-containing norbornenecompound represented by formula (I) of claim 1; (B) said copolymercomprises:(i) constituent units derived from said ethylene in an amountof 30 to 92% by mol, (ii) constituent units derived from said α-olefinof 3 to 20 carbon atoms in an mount of 6 to 70% by mol, and (iii)constituent units derived from said chain polyene group-containingnorbornene compound represented by formula (I) of claim 1 in an amountof 0.1 to 30% by mol, in which (iv) the molar ratio of (i) saidconstituent units derived from said ethylene/(ii) said constituent unitsderived from said α-olefin of 3 to 20 carbon atoms is in the range of40/60 to 92/8; (C) said constituent unit derived from the chainpolyene-group containing norbornene compound represented by formula (I)of claim 1 has a structure represented by the following formula:##STR47## wherein n is an integer of 1 to 5, R¹ is an alkyl group of 1to 5 carbon atoms, and R² and R³ are each independently a hydrogen atomor an alkyl group of 1 to 5 carbon atoms; and (D) said copolymer has anintrinsic viscosity (η), as measured in Decalin at 135° C., of 0.05 to10 dl/g.
 4. A process for preparing an unsaturated ethylene copolymer asclaimed in claim 3, comprising copolymerizing:(i) ethylene, (ii) anα-olefin of 3 to 20 carbon atoms, and (iii) at least one chain polyenegroup-containing norbornene compound represented by formula (I) of claim1, in the presence of a catalyst formed from a transition metalcompound, an organoaluminum compound and/or an ionizable ionic compound.5. An unsaturated ethylene copolymer wherein:(A) said copolymer is arandom copolymer of(i) ethylene, (ii) an α-olefin of 3 to 20 carbonatoms, and (iii) at least one chain polyene group-containing norbornenecompound represented by formula (I) of claim 1 and at least one chainpolyene group-containing norbornene compound represented by thefollowing formula (I-a) in a smaller amount than that of the chainpolyene group-containing norbornene compound (I), ##STR48## wherein n,R¹, R² and R³ have the same meaning as in the formula (I); (B) The saidcopolymer comprises:(i) constituent units derived from said ethylene inan amount of 30 to 92% by mol, (ii) constituent units derived from saidα-olefin 3 to 20 carbon atoms in an amount of 6 to 70% by mol, and (iii)constituent units derived from said chain polyene group-containingnorbornene compound represented by formula (I) of claim 1 andconstituent units derived from said chain polyene group-containingnorbornene compound represented by the formula (I-a) in a smaller amountthan that of the chain polyene group-containing norbornene compound (I)in the total amount of 0.1 to 30% by mol, in which (iv) the molar ratioof (i) said constituent units derived from said ethylene/(ii) saidconstituent units derived from said α-olefin of 3 to 20 carbon atoms isin the range of 40/60 to 92/8; (C) said constituent unit derived fromthe chain polyene-group containing norbornene compound represented bythe above formula (I) has a structure represented by formula (I) ofclaim 1, and said constituent unit derived from said chain polyene-groupcontaining norbornene compound represented by the above formula (I-a)has a structure represented by the following formula (II-a): ##STR49##wherein n, R¹, R², and R³ have the same meanings as in the formula (II)of claim 3; and (D) said copolymer has an intrinsic viscosity (η), asmeasured in Decalin at 135° C., of 0.05 to 10 dl/g.
 6. A process forpreparing an unsaturated ethylene copolymer as claimed in claim 5,comprising copolymerizing(i) ethylene, (ii) an α-olefin of 3 to 20carbon atoms, and (iii) at least one chain polyene group-containingnorbornene compound represented by the above formula (I) and at leastone chain polyene group-containing norbornene compound represented bythe above formula (I-a), in the presence of a catalyst formed from atransition metal compound, an organoaluminum compound and/or anionizable ionic compound.
 7. The chain polyene group-containingnorbornene compound of claim 1 represented by the formula (I): ##STR50##wherein n is an integer of 1 to 5, R¹ is an alkyl group of 1 to 2 carbonatoms, and R² is an alkyl group of 1 to 3 carbon atoms and R³ is ahydrogen atom or an alkyl group of 1 to 3 carbon atoms.
 8. The chainpolyene group-containing norbornene compound represented by the formula(I) of claim 7, in which n is an integer of 1 to
 3. 9. The process ofclaim 2 for preparing a chain polyene group-containing norbornenecompound comprising reacting cyclopentadiene with a branched chainpolyene compound represented by the formula (III): ##STR51## wherein nis an integer of 1 to 5, R¹ is an alkyl group of 1 to 2 carbon atoms, R²is an alkyl group of 1 to 3 carbon atoms and R³ is a hydrogen atom andan alkyl group of 1 to 3 carbon atoms.
 10. The process of claim 9 forpreparing a chain polyene group-containing norbornene compoundcomprising reacting cyclopentadiene with a branched chain polyenecompound represented by the formula (II) of claim 9 in which n is aninteger of 1 to 3.